Use of n-functionalized alkoxy pyrazole compounds as nitrification inhibitors

ABSTRACT

The present invention relates to the use of novel nitrification inhibitors of formula I, which are N-functionalized alkoxy pyrazole compounds. Moreover, the invention relates to the use of compounds of formula I as nitrification inhibitors, i.e. for reducing nitrification, as well as agrochemical mixtures and compositions comprising the nitrification inhibitors of formula I.

CROSS-REFERENCE TO RELATED APPLICATIONS

This is continuation of U.S. patent application Ser. No. 16/969,030,filed Aug. 11, 2020, which is a U.S. national phase of InternationalApplication No. PCT/EP2019/055006, filed Feb. 28, 2019, which claims thebenefit of European Patent Application No. 18159321.1, filed Feb. 28,2018.

DESCRIPTION

The present invention relates to novel nitrification inhibitors offormula I, which are N-functionalized alkoxy pyrazole compounds.Moreover, the invention relates to the use of compounds of formula I asnitrification inhibitors, i.e. for reducing nitrification, as well asagrochemical mixtures and compositions comprising the nitrificationinhibitors of formula I. Further encompassed by the present inventionare methods for reducing nitrification, said methods comprising thetreatment of plants, soil and/or loci where the plant is growing or isintended to grow with said nitrification inhibitor and methods fortreating a fertilizer or a composition by applying said nitrificationinhibitor.

Nitrogen is an essential element for plant growth and reproduction.About 25% of the plant available nitrogen in soils (ammonium andnitrate) originate from decomposition processes (mineralization) oforganic nitrogen compounds such as humus, plant and animal residues andorganic fertilizers. Approximately 5% derive from rainfall. On a globalbasis, the biggest part (70%), however, is supplied to the plant byinorganic nitrogen fertilizers. The mainly used nitrogen fertilizerscomprise ammonium compounds or derivatives thereof, i.e. nearly 90% ofthe nitrogen fertilizers applied worldwide is in the NH₄ ⁺ form(Subbarao et al., 2012, Advances in Agronomy, 114, 249-302). This is,inter alia, due to the fact that NH₄ ⁺ assimilation is energeticallymore efficient than assimilation of other nitrogen sources such as NO₃⁻.

Moreover, being a cation, NH₄ ⁺ is held electrostatically by thenegatively charged clay surfaces and functional groups of soil organicmatter. This binding is strong enough to limit NH₄ ⁺-loss by leaching togroundwater. By contrast, NO₃ ⁻, being negatively charged, does not bindto the soil and is liable to be leached out of the plants' root zone. Inaddition, nitrate may be lost by denitrification which is themicrobiological conversion of nitrate and nitrite (NO₂) to gaseous formsof nitrogen such as nitrous oxide (N₂O) and molecular nitrogen (N₂).

However, ammonium (NH₄ ⁺) compounds are converted by soil microorganismsto nitrates (NO₃ ⁻) in a relatively short time in a process known asnitrification. The nitrification is carried out primarily by two groupsof chemolithotrophic bacteria, ammonia-oxidizing bacteria (AOB) of thegenus Nitrosomonas and Nitrobacter, which are ubiquitous component ofsoil bacteria populations. The enzyme, which is essentially responsiblefor nitrification is ammonia monooxygenase (AMO), which was also foundin ammonia-oxidizing archaea (Subbarao et al., 2012, Advances inAgronomy, 114, 249-302).

The nitrification process typically leads to nitrogen leakage andenvironmental pollution. As a result of the various losses,approximately 50% of the applied nitrogen fertilizers are lost duringthe year following fertilizer addition (see Nelson and Huber;Nitrification inhibitors for corn production (2001), National CornHandbook, Iowa State University).

As countermeasure, the use of nitrification inhibitors, mostly togetherwith fertilizers, was suggested. Suitable nitrification inhibitorsinclude biological nitrification inhibitors (BNIs) such as linoleicacid, alpha-linolenic acid, methyl p-coumarate, methyl ferulate, MHPP,Karanjin, brachialacton or the p-benzoquinone sorgoleone (Subbarao etal., 2012, Advances in Agronomy, 114, 249-302). Further suitablenitrification inhibitors are synthetic chemical inhibitors such asnitrapyrin, dicyandiamide (DCD), 3,4-dimethyl pyrazole phosphate (DMPP),4-amino-1,2,4-triazole hydrochloride (ATC), 1-amido-2-thiourea (ASU),2-amino-4-chloro-6-methylpyrimidine (AM),5-ethoxy-3-trichloromethyl-1,2,4-thiodiazole (terrazole), or2-sulfanilamidothiazole (ST) (Slangen and Kerkhoff, 1984, Fertilizerresearch, 5(1), 1-76).

However, many of these inhibitors only work sub-optimal. In addition,the world population is expected to grow significantly in the next 20-30years, and, therefore, food production in sufficient quantities andquality is necessary. In order to achieve this, the use of nitrogenfertilizers would have to double by 2050. For environmental reasons,this is not possible, since nitrate levels in drinking water,eutrophication of surface water and gas emissions into the air havealready reached critical levels in many places, causing watercontamination and air pollution. However, fertilizer efficiencyincreases significantly and less fertilizer may therefore be applied, ifnitrification inhibitors are used. Therefore, there is a clear need fornovel nitrification inhibitors, as well as for methods using them.

Sharma et al. (J P Sharma, H K Taneja, S S Tomar Pesticide ResearchJournal, 2006, 18(1), 7-11) inter alia discloses3-ethoxy-5-methylpyrazole as nitrification inhibitor. However, it hasbeen found that this compound has a high volatility and is thereforedisadvantageous for long-term applications.

It was an object of the present invention to provide improvednitrification inhibitors.

In particular, it was an object of the present invention to providenitrification inhibitors, which have a high activity as nitrificationinhibitors, but at the same time have a reduced volatility and toxicityin comparison to the nitrification inhibitors described in the priorart.

Furthermore, it was an object of the present invention to providenitrification inhibitors, which may cost-effectively be prepared, andwhich are environmentally safe.

It has surprisingly been found that these objects can be achieved byusing the nitrification inhibitors according to the present invention,which are N-functionalized alkoxy pyrazole compounds of formula I

-   or the salts, stereoisomers, tautomers, or N-oxides thereof,-   wherein-   R¹ is H, C₁-C₆-alkyl, C₃-C₆-cycloalkyl, benzyl, allyl,    CHR^(a)C(═O)OR^(b), CHR^(a)C(═O)NR^(b)R^(c) or phenyl, wherein said    phenyl group is unsubstituted or substituted by one or more, same or    different substituents R^(x);-   R² is halogen, C₁-C₆-alkyl, C₃-C₆-cycloalkyl, benzyl, allyl,    propargyl, or phenyl, wherein said phenyl group is unsubstituted or    substituted by one or more, same or different substituents R^(x);-   R^(N) is C₁-C₆-akyl C₃-C₆-cycloalkyl, benzyl, allyl, propargyl, or    phenyl, wherein said groups are unsubstituted or substituted by one    or more, same or different substituents R^(y);    -   CHR^(a)C(═O)OR^(b), CHR^(a)C(═O)NR^(b)R^(c),        CH(C(═O)OR^(b))CH₂(C(═O)OR^(b));    -   C(═O)R^(d), C(═O)OR^(b), C(═O)NR^(b)R^(c), CHR^(a)OR^(b), or        CHR^(a)NR^(e)(C═O)R^(f);-   and wherein-   R^(a) is H, C₁-C₄-alkyl, C₁-C₄-haloalkyl, C₃-C₈-cycloalkyl, phenyl,    or phenyl-C₁-C₂-alkyl;-   R^(b) is H, C₁-C₄-alkyl, C₁-C₄-haloalkyl, C₃-C₈-cycloalkyl, phenyl,    or phenyl-C₁-C₂-alkyl;-   R^(c) is H, C₁-C₄-alkyl, C₁-C₄-haloalkyl, or phenyl;-   R^(d) is H, C₁-C₈-alkyl, C₂-C₈-alkenyl, C₂-C₈-alkynyl, phenyl, or    phenyl-C₁-C₂-alkyl, wherein these groups are unsubstituted or    substituted by a group COOH;-   R^(e) is H, C₁-C₄-alkyl, C₃-C₈-cycloalkyl, or C₆-C₁₀-aryl;-   R^(f) is H, or C₁-C₄-alkyl;-   R^(x) is halogen, C₁-C₄-alkyl, C₁-C₄-haloalkyl, C₁-C₄-alkoxy, or    C₁-C₄-haloalkoxy;-   R^(y) is halogen, CN, OH, NO₂, COOH, NR^(b)R^(c), NR^(b)(C═O)R,    C(═O)NR^(b)R^(c), C₁-C₄-alkyl, C₁-C₄-haloalkyl, C₁-C₄-alkoxy,    C₁-C₄-haloalkoxy, C₁-C₄-alkylcarbonyl, C₁-C₄-alkylcarboxy,    C₁-C₄-alkylthio, C₁-C₄-alkylsulfonyl, and S(O)₂NR^(b)R^(c);-   n is 0, 1, or 2.

The inventors surprisingly found that by applying the compounds offormula I as defined above and hereinafter the nitrification of ammoniumto nitrate can significantly be reduced.

Furthermore, the compounds of formula I surprisingly exhibit a lowtoxicity and a low volatility.

Thus, according to one embodiment, the present invention relates to theuse of an N-functionalized alkoxy pyrazole compound of formula I

-   or a salt, stereoisomer, tautomer, or N-oxide thereof as a    nitrification inhibitor,-   wherein-   R¹ is H, C₁-C₆-alkyl, C₃-C₆-cycloalkyl, benzyl, allyl,    CHR^(a)C(═O)OR^(b), CHR^(a)C(═O)NR^(b)R^(c) or phenyl, wherein said    phenyl group is unsubstituted or substituted by one or more, same or    different substituents R^(x);-   R² is halogen, C₁-C₆-alkyl, C₃-C₆-cycloalkyl, benzyl, allyl,    propargyl, or phenyl, wherein said phenyl group is unsubstituted or    substituted by one or more, same or different substituents R^(x);-   R^(N) is C₁-C₆-akyl C₃-C₆-cycloalkyl, benzyl, allyl, propargyl, or    phenyl, wherein said groups are unsubstituted or substituted by one    or more, same or different substituents R^(y);    -   CHR^(a)C(═O)OR^(b), CHR^(a)C(═O)NR^(b)R^(c),        CH(C(═O)OR^(b))CH₂(C(═O)OR^(b));    -   C(═O)R^(d), C(═O)OR^(b), C(═O)NR^(b)R^(c), CHR^(a)OR^(b), or        CHR^(a)NR^(e)(C═O)R^(f);    -   and wherein-   R^(a) is H, C₁-C₄-alkyl, C₁-C₄-haloalkyl, C₃-C₈-cycloalkyl, phenyl,    or phenyl-C₁-C₂-alkyl;-   R^(b) is H, C₁-C₄-alkyl, C₁-C₄-haloalkyl, C₃-C₈-cycloalkyl, phenyl,    or phenyl-C₁-C₂-alkyl;-   R^(c) is H, C₁-C₄-alkyl, C₁-C₄-haloalkyl, or phenyl;-   R^(d) is H, C₁-C₈-alkyl, C₂-C₈-alkenyl, C₂-C₈-alkynyl, phenyl, or    phenyl-C₁-C₂-alkyl, wherein these groups are unsubstituted or    substituted by a group COOH;-   R^(e) is H, C₁-C₄-alkyl, C₃-C₈-cycloalkyl, or C₆-C₁₀-aryl;-   R^(f) is H, or C₁-C₄-alkyl;-   R^(x) is halogen, C₁-C₄-alkyl, C₁-C₄-haloalkyl, C₁-C₄-alkoxy, or    C₁-C₄-haloalkoxy;-   R^(y) is halogen, CN, OH, NO₂, COOH, NR^(b)R^(c), NR^(b)(C═O)R,    C(═O)NR^(b)R^(c), C₁-C₄-alkyl, C₁-C₄-haloalkyl, C₁-C₄-alkoxy,    C₁-C₄-haloalkoxy, C₁-C₄-alkylcarbonyl, C₁-C₄-alkylcarboxy,    C₁-C₄-alkylthio, C₁-C₄-alkylsulfonyl, and S(O)₂NR^(b)R^(c);-   n is 0, 1, or 2.

In one preferred embodiment of said use, in said compound of formula I

-   R¹ is C₁-C₆-alkyl, benzyl, or allyl.

In another preferred embodiment of said use, in said compound of formulaI

-   n is 0, i.e. R² is absent, or-   n is 1, and R² is C₁-C₃-alkyl or phenyl.

In another preferred embodiment of said use, in said compound of formulaI

-   R^(N) is C(═O)R^(d), CHR^(a)C(═O)ORD, CHR^(a)C(═O)NR^(b)R^(c),    CH(C(═O)OR^(b))CH₂(C(═O)OR^(b)), or CHR^(a)NR^(c)(C═O) R^(f).

In another preferred embodiment of said use, in said compound of formulaI

-   R^(a) is H;-   R^(b) is H or C₁-C₄-alkyl;-   R^(c) is H or C₁-C₄-alkyl;-   R^(d) is C₁-C₃-alkyl;-   R^(e) is H;-   R^(f) is H or CH₃.

In a further aspect, the present invention relates to a composition foruse in reducing nitrification comprising at least one compound offormula I as defined above and at least one carrier.

In a further aspect, the present invention relates to an agrochemicalmixture comprising at least one fertilizer and at least one compound offormula I as defined above; or at least one fertilizer and a compositionas mentioned above for use in reducing nitrification.

In a preferred embodiment, said compound of formula I as defined aboveis used in combination with a fertilizer for reducing nitrification. Ina further specific embodiment, said compound of formula I as definedabove is used for reducing nitrification in combination with afertilizer in the form of an agrochemical mixture as mentioned above. Ina further preferred embodiment, said reduction of nitrification asmentioned above occurs in or on a plant, in the root zone of a plant, inor on soil or soil substituents and/or at the locus where a plant isgrowing or is intended to grow.

In another aspect, the present invention relates to a method forreducing nitrification, comprising treating a plant growing on soil orsoil substituents and/or the locus or soil or soil substituents wherethe plant is growing or is intended to grow with at least one compoundof formula I as defined above, or with an agrochemical composition asdefined above. In a preferred embodiment of the method, the plant and/orthe locus or soil or soil substituents where the plant is growing or isintended to grow is additionally provided with a fertilizer. In afurther preferred embodiment of the method, the application of thenitrification inhibitor, i.e. the compound of formula I, and of saidfertilizer is carried out simultaneously or with a time lag. In aparticularly preferred embodiment, said time lag is an interval of 1day, 2 days, 3 days, 1 week, 2 weeks or 3 weeks. In case of applicationwith a time lag, the nitrification inhibitor may be applied first andthen the fertilizer. In a further preferred embodiment of the method, ina first step the nitrification inhibitor as defined above is applied toseeds, to a plant and/or to the locus where the plant is growing or isintended to grow and in a second step the fertilizer is applied to aplant and/or to the locus where the plant is growing or is intended togrow, wherein the application of a said nitrification inhibitor in thefirst step and the fertilizer in the second step is carried out with atime lag of at least 1 day, 2 days, 3 days, 4 days, 5, days, 6 days, 1week, 2 weeks or 3 weeks. In other embodiments of application with atime lag, a fertilizer may be applied first and then the nitrificationinhibitor as defined above may be applied. In a further preferredembodiment of the method, in a first step a fertilizer is applied to aplant and/or to the locus where the plant is growing or is intended togrow and in a second step the nitrification inhibitor as defined aboveis applied to seeds, to a plant and/or to the locus where the plant isgrowing or is intended to grow, wherein the application of a saidfertilizer in the first step and said nitrification inhibitor in thesecond step is carried out with a time lag of at least 1 day, 2 days, 3days, 4 days, 5, days, 6 days, 1 week, 2 weeks or 3 weeks.

In another aspect, the present invention relates to a method fortreating a fertilizer, comprising the application of a nitrificationinhibitor as defined above; or to a method for treating a composition asdefined above, comprising the application of a nitrification inhibitoras defined above.

In a preferred embodiment of the use, the agrochemical mixture or methodof the invention, said fertilizer is a solid or liquidammonium-containing inorganic fertilizer such as NPK fertilizer,ammonium nitrate, calcium ammonium nitrate, ammonium sulfate nitrate,ammonium sulfate or ammonium phosphate; a solid or liquid organicfertilizer such as liquid manure, semi-liquid manure, biogas manure,stable manure and straw manure, worm castings, compost, seaweed orguano, or an urea-containing fertilizer such as urea, formaldehyde urea,anhydrous ammonium, urea ammonium nitrate (UAN) solution, urea sulphur,urea based NPK-fertilizers, or urea ammonium sulfate.

In a further preferred embodiment of the use or method of the invention,said plant is an agricultural plant such as wheat, barley, oat, rye,soybean, corn, potatoes, oilseed, rape, canola, sunflower, cotton, sugarcane, sugar beet, rice, or a vegetable such as spinach, lettuce,asparagus, or cabbages; or sorghum; a silvicultural plant; an ornamentalplant; or a horticultural plant, each in its natural or in a geneticallymodified form.

The compounds of formula I can be prepared by standard processes oforganic chemistry.

Suitable methods for preparing pyrazole compounds in general aredescribed in “Progress in Heterocyclic Chemistry”, Vol. 27, G. W.Gribble, J. A. Joule, Elsevier, 2015, Chapter 5.4.2.

The OR¹ group may be introduced by selecting suitable starting materialsfor the pyrazole ring formation.

A general method for the synthesis of 3-alkoxy-pyrazoles comprises thereaction between hydrazine hydrochloride and various β-ketoesters asdescribed by, for example: a) Sadrine Guillou, Frédéric J. Bonhomme,Yves L. Janin, Synthesis 2008, 3504-3508; or b) in WO 2010/015657 A2,and as shown below:

R^(A) and R^(B) may be hydrogen or may have any of the meaning providedabove for R².

Mazaahir Kidwai, Arti Jain, Roona Poddar, Journal of OrganometallicChemistry 696 (2011) 1939-1944 showed that 3-alkoxy-pyrazolessubstituted on N are directly obtained if in the above reactionN-substituted hydrazine derivatives are used instead of hydrazine.

Further, the 3-alkoxy-group can be introduced by alkylating a suitablehydroxypyrazole derivative as described e.g. by a) D. Piomelli andcoworkers, Synthesis 2016, 2739-2756, or b) Sandrine Guillou, Yves L.Janin, Chem. Eur. J. 2010, 16, 4669-4677.

Diverse methods to synthesise pyrazoles bearing the alkoxy-group in theposition 4 were described by William F. Vernier, Laurent Gomez,Tetrahedron Letters 2017, 4587-4590.

If RNs, e.g., C₁-C₆-akyl the R^(N)-substituent may be introduced byreacting a compound of formula II with a compound of formula III,wherein LG represents a leaving group, according to the followingscheme.

For example, various alkylation or acylation reagents R^(N)-LG can beused in analogy to N-methylation of 3-methoxy-4-nitro-1H-pyrazole withmethyliodide, which affords 1-methyl-3-methoxy-4-nitro-1H-pyrazole asdescribed in WO 2009/153589 A1 or in WO 2011/048082 A1.

Introduction of a CH₂OH group as R^(N) can be performed by reacting thepyrazole with formaldehyde, as described by Simona Lupsor, Mircea lovuand Florin Aonofriesei, Med. Chem. Res. 2012, 3035-3042.

Similarly, a Michael addition may be performed with a maleic acidderivative forming the substituent R^(N).

Methods for preparing pyrazole compounds, wherein R^(N) is, e.g., aformamide are described in DE 10 2011 120 098 A1 and WO 2013/079197 A1.

It is to be understood that, before the substituent R^(N) is introduced,different tautomers may be formed resulting in the formation of anisomer mixture after the introduction of the substituent R^(N). Incertain preferred embodiments of the invention, such isomer mixtures maybe used as nitrification inhibitors.

The substituent R² may be introduced by standard reactions includingaromatic substitution reactions, or by selecting suitable startingmaterials for the pyrazole ring formation.

Before describing in detail exemplary embodiments of the presentinvention, definitions important for understanding the present inventionare given.

As used in this specification and in the appended claims, the singularforms of “a” and “an” also include the respective plurals unless thecontext clearly dictates otherwise. In the context of the presentinvention, the terms “about” and “approximately” denote an interval ofaccuracy that a person skilled in the art will understand to stillensure the technical effect of the feature in question. The termtypically indicates a deviation from the indicated numerical value of±20%, preferably ±15%, more preferably ±10%, and even more preferably±5%. It is to be understood that the term “comprising” is not limiting.For the purposes of the present invention the term “consisting of” isconsidered to be a preferred embodiment of the term “comprising of”. Ifhereinafter a group is defined to comprise at least a certain number ofembodiments, this is meant to also encompass a group, which preferablyconsists of these embodiments only. Furthermore, the terms “first”,“second”, “third” or “(a)”, “(b)”, “(c)”, “(d)” etc. and the like in thedescription and in the claims, are used for distinguishing betweensimilar elements and not necessarily for describing a sequential orchronological order. It is to be understood that the terms so used areinterchangeable under appropriate circumstances and that the embodimentsof the invention described herein are capable of operation in othersequences than described or illustrated herein. In case the terms“first”, “second”, “third” or “(a)”, “(b)”, “(c)”, “(d)”, “i”, “ii” etc.relate to steps of a method or use or assay there is no time or timeinterval coherence between the steps, i.e. the steps may be carried outsimultaneously or there may be time intervals of seconds, minutes,hours, days, weeks, months or even years between such steps, unlessotherwise indicated in the application as set forth herein above orbelow.

It is to be understood that this invention is not limited to theparticular methodology, protocols, reagents etc. described herein asthese may vary. It is also to be understood that the terminology usedherein is for the purpose of describing particular embodiments only, andis not intended to limit the scope of the present invention that will belimited only by the appended claims. Unless defined otherwise, alltechnical and scientific terms used herein have the same meanings ascommonly understood by one of ordinary skill in the art.

The term “nitrification inhibitor” is to be understood in this contextas a chemical substance, which slows down or stops the nitrificationprocess. Nitrification inhibitors accordingly retard the naturaltransformation of ammonium into nitrate, by inhibiting the activity ofbacteria such as Nitrosomonas spp. The term “nitrification” as usedherein is to be understood as the biological oxidation of ammonia (NH₃)or ammonium (NH₄ ⁺) with oxygen into nitrite (NO₂ ⁻) followed by theoxidation of these nitrites into nitrates (NO₃ ⁻) by microorganisms.Besides nitrate (NO₃ ⁻) nitrous oxide is also produced throughnitrification.

Nitrification is an important step in the nitrogen cycle in soil. Theinhibition of nitrification may thus also reduce N₂O losses. The termnitrification inhibitor is considered equivalent to the use of such acompound for inhibiting nitrification.

The term “compound(s) according to the invention”, or “compounds offormula I” comprises the compound(s) as defined herein as well as astereoisomer, salt, tautomer or N-oxide thereof. The term “compound(s)of the present invention” is to be understood as equivalent to the term“compound(s) according to the invention”, therefore also comprising astereoisomer, salt, tautomer or N-oxide thereof.

Depending on the substitution pattern, the compounds according to theinvention may have one or more centers of chirality, in which case theyare present as mixtures of enantiomers or diastereomers. The inventionprovides both the single pure enantiomers or pure diastereomers of thecompounds according to the invention, and their mixtures and the useaccording to the invention of the pure enantiomers or pure diastereomersof the compounds according to the invention or their mixtures. Suitablecompounds according to the invention also include all possiblegeometrical stereoisomers (cis/trans isomers) and mixtures thereof.Cis/trans isomers may be present with respect to an alkene,carbon-nitrogen double-bond or amide group. The term “stereoisomer(s)”encompasses both optical isomers, such as enantiomers or diastereomers,the latter existing due to more than one center of chirality in themolecule, as well as geometrical isomers (cis/trans isomers). Thepresent invention relates to every possible stereoisomer of thecompounds of formula I, i.e. to single enantiomers or diastereomers, aswell as to mixtures thereof.

The compounds of formula I may be amorphous or may exist in one or moredifferent crystalline states (polymorphs) which may have differentmacroscopic properties such as stability or show different biologicalproperties such as activities. The present invention relates toamorphous and crystalline compounds of formula I, mixtures of differentcrystalline states of the respective compound I, as well as amorphous orcrystalline salts thereof.

Salts of the compounds of the formula I are preferably agriculturallyacceptable salts. They can be formed in a customary manner, e.g. byreacting the compound with an acid of the anion in question if thecompound of formula I has a basic functionality. Agriculturally usefulsalts of the compounds of formula I encompass especially the acidaddition salts of those acids whose cations and anions, respectively,have no adverse effect on the mode of action of the compounds of formulaI. Anions of useful acid addition salts are primarily chloride, bromide,fluoride, hydrogensulfate, sulfate, dihydrogenphosphate,hydrogenphosphate, phosphate, nitrate, bicarbonate, carbonate,hexafluorosilicate, hexafluorophosphate, benzoate, and preferablyphosphate and the anions of C₁-C₄-alkanoic acids, preferably formate,acetate, propionate and butyrate. They can preferably be formed byreacting compounds of formula I with an acid of the corresponding anion,preferably of hydrochloric acid, hydrobromic acid, sulfuric acid,phosphoric acid or nitric acid.

The term “N-oxide” includes any compound of formula I, wherein atertiary nitrogen atom, e.g. the pyridine nitrogen atom, is oxidized toan N-oxide moiety.

Tautomers of the compounds of formula I may be present, if, e.g., anyone of the substituents at the aromatic ring has tautomeric forms.Preferred tautomers include keto-enol tautomers.

The organic moieties mentioned in the above definitions of the variablesare—like the term halogen—collective terms for individual listings ofthe individual group members. The prefix C_(n)-C_(m) indicates in eachcase the possible number of carbon atoms in the group.

The term “halogen” denotes in each case fluorine, bromine, chlorine oriodine, in particular fluorine, chlorine or bromine.

The term “alkyl” as used herein denotes in each case a straight-chain orbranched alkyl group having usually from 1 to 4 carbon atoms, preferablyfrom 1 to 3 carbon atoms. Preferred alkyl groups include methyl, ethyl,n-propyl, iso-propyl, n-butyl, 2-butyl, iso-butyl, tert-butyl, n-pentyl,1-methylbutyl, 2-methylbutyl, 3-methylbutyl, and 2,2-dimethylpropyl.Methyl, ethyl, n-propyl and iso-propyl are particularly preferred.

The term “haloalkyl” as used herein denotes in each case astraight-chain or branched alkyl group having usually from 1 to 4 carbonatoms, preferably from 1 to 3 carbon atoms, especially 1 or 2 carbonatoms, wherein the hydrogen atoms of this group are partially or totallyreplaced with halogen atoms. Preferred haloalkyl moieties are selectedfrom C₁-C₄-haloalkyl, more preferably from C₁-C₃-haloalkyl orC₁-C₂-haloalkyl, in particular from C₁-C₂-fluoroalkyl such asfluoromethyl, difluoromethyl, trifluoromethyl, 1-fluoroethyl,2-fluoroethyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyl,pentafluoroethyl, and the like. Trifluormethyl is particularly preferredaccording to the invention.

The term “alkoxy” as used herein denotes in each case a straight-chainor branched alkyl group, which is bonded via an oxygen group, havingusually from 1 to 4 carbon atoms, preferably from 1 to 3 carbon atoms,especially 1 or 2 carbon atoms. Examples of alkoxy groups are methoxy,ethoxy, n-propoxy, iso-propoxy, n-butyloxy, 2-butyloxy, iso-butyloxy,tert.-butyloxy, and the like.

The term “haloalkoxy” as used herein denotes in each case astraight-chain or branched alkoxy group having usually from 1 to 4carbon atoms, preferably from 1 to 3 carbon atoms, especially 1 or 2carbon atoms, wherein the hydrogen atoms of this group are partially ortotally replaced with halogen atoms, in particular fluorine atoms.Preferred haloalkoxy moieties include C₁-C₄-haloalkoxy, in particularC₁-C₂-fluoroalkoxy, such as fluoromethoxy, difluoromethoxy,trifluoromethoxy, 1-fluoroethoxy, 2-fluoroethoxy, 2,2-difluoroethoxy,2,2,2-trifluoroethoxy, 2-chloro-2-fluoroethoxy,2-chloro-2,2-difluoro-ethoxy, 2,2dichloro-2-fluorethoxy,2,2,2-trichloroethoxy, pentafluoroethoxy and the like.

The term “alkenyl” as used herein denotes in each case an at leastsingly unsaturated hydrocarbon radical, i.e. a hydrocarbon radicalhaving at least one carbon-carbon double bond, having usually 2 to 4carbon atoms, preferably 2 or 3 carbon atoms, e.g. vinyl, allyl(2-propen-1-yl), 1-propen-1-yl, 2-propen-2-yl, methallyl(2-methylprop-2-en-1-yl), 2-buten-1-yl, 3-buten-1-yl, 2-penten-1-yl,3-penten-1-yl, 4-penten-1-yl, 1-methylbut-2-en-1-yl,2-ethylprop-2-en-1-yl and the like.

The term “alkynyl” as used herein denotes in each case a hydrocarbonradical having at least one carbon-carbon triple bond and having usually2 to 4, preferably 2 or 3 carbon atoms or 3 or 4 carbon atoms, e.g.ethynyl, propargyl (2-propyn-1-yl, also referred to as prop-2-yn-1-yl),1-propyn-1-yl (also referred to as prop-1-yn-1-yl),1-methylprop-2-yn-1-yl, 2-butyn-1-yl, 3-butyn-1-yl, 1-pentyn-1-yl,3-pentyn-1-yl, 4-pentyn-1-yl, 1-methylbut-2-yn-1-yl,1-ethylprop-2-yn-1-yl and the like. A preferred alkynyl group accordingto the invention is ethynyl.

The term “phenylalkyl” as used herein denotes a phenyl group, which isbonded via an alkyl group, preferably a C₁-C₂-alkyl group, in particulara methyl group (=phenylmethyl), to the remainder of the molecule. Themost preferred phenylalkyl group is benzyl.

The term “cycloalkyl” as used herein and in the cycloalkyl moieties ofcycloalkoxy and cycloalkylthio denotes in each case a monocycliccycloaliphatic radical having usually from 3 to 10 or from 3 to 6 carbonatoms, such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl,cycloheptyl, cyclooctyl, cyclononyl and cyclodecyl and preferablycyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl.

The term “alkylcarbonyl” refers to an alkyl group as defined above,which is bonded via the carbon atom of a carbonyl group (C═O) to theremainder of the molecule.

The term “alkylcarboxy” as used herein refers to a straight-chain orbranched saturated alkyl group having 1 to 10 carbon atoms, preferably 1to 4 carbon atoms (═C₁-C₄-alkylcarboxy), preferably 1 to 3 carbon atoms,which is bonded via the carboxyl group at any position in the alkylgroup.

The term “alkylthio” “(alkylsulfanyl: alkyl-S—)” as used herein refersto a straight-chain or branched saturated alkyl group having 1 to 10carbon atoms, preferably 1 to 4 carbon atoms (═C₁-C₄-alkylthio), morepreferably 1 to 3 carbon atoms, which is attached via a sulfur atom.

The term “alkylsulfonyl” (alkyl-S(═O)₂—) as used herein refers to astraight-chain or branched saturated alkyl group having 1 to 10 carbonatoms, preferably 1 to 4 carbon atoms (═C₁-C₄-alkylsulfonyl), preferably1 to 3 carbon atoms, which is bonded via the sulfur atom of the sulfonylgroup at any position in the alkyl group.

As has been set out above, the present invention concerns in one aspectthe use of an N-functionalized alkoxy pyrazole compound of formula I

-   or a salt, stereoisomer, tautomer, or N-oxide thereof as a    nitrification inhibitor,-   wherein-   R¹ is H, C₁-C₆-alkyl, C₃-C₆-cycloalkyl, benzyl, allyl,    CHR^(a)C(═O)OR^(b), CHR^(a)C(═O)NR^(b)R^(c) or phenyl, wherein said    phenyl group is unsubstituted or substituted by one or more, same or    different substituents R^(x);-   R² is halogen, C₁-C₆-alkyl, C₃-C₆-cycloalkyl, benzyl, allyl,    propargyl, or phenyl, wherein said phenyl group is unsubstituted or    substituted by one or more, same or different substituents R^(x);-   R^(N) is C₁-C₆-akyl C₃-C₆-cycloalkyl, benzyl, allyl, propargyl, or    phenyl, wherein said groups are unsubstituted or substituted by one    or more, same or different substituents R^(y);    -   CHR^(a)C(═O)OR^(b), CHR^(a)C(═O)NR^(b)R^(c),        CH(C(═O)OR^(b))CH₂(C(═O)OR^(b));    -   C(═O)R^(d), C(═O)OR^(b), C(═O)NR^(b)R^(c), CHR^(a)OR^(b), or        CHR^(a)NR^(c)(C═O)R^(f);-   and wherein-   R^(a) is H, C₁-C₄-alkyl, C₁-C₄-haloalkyl, C₃-C₈-cycloalkyl, phenyl,    or phenyl-C₁-C₂-alkyl;-   R^(b) is H, C₁-C₄-alkyl, C₁-C₄-haloalkyl, C₃-C₈-cycloalkyl, phenyl,    or phenyl-C₁-C₂-alkyl;-   R^(c) is H, C₁-C₄-alkyl. C₁-C₄-haloalkyl, or phenyl;-   R^(d) is H, C₁-C₈-alkyl, C₂-C₈-alkenyl, C₂-C₈-alkynyl, phenyl, or    phenyl-C₁-C₂-alkyl, wherein these groups are unsubstituted or    substituted by a group COOH;-   R^(e) is H, C₁-C₄-alkyl, C₃-C₈-cycloalkyl, or C₆-C₁₀-aryl;-   R^(f) is H, or C₁-C₄-alkyl;-   R^(x) is halogen, C₁-C₄-alkyl, C₁-C₄-haloalkyl, C₁-C₄-alkoxy, or    C₁-C₄-haloalkoxy;-   R^(y) is halogen, CN, OH, NO₂, COOH, NR^(b)R^(c), NR^(b)(C═O)R,    C(═O)NR^(b)R^(c), C₁-C₄-alkyl, C₁-C₄-haloalkyl, C₁-C₄-alkoxy,    C₁-C₄-haloalkoxy, C₁-C₄-alkylcarbonyl, C₁-C₄-alkylcarboxy,    C₁-C₄-alkylthio, C₁-C₄-alkylsulfonyl, and S(O)₂NR^(b)R^(c);-   n is 0, 1, or 2.

It is to be understood that if n is 2, two R²-substituents are presentwhich are independently selected from the group of substituents definedabove for R².

Preferred embodiments regarding the compounds of formula I, which arerelevant for all aspects of the invention, are defined hereinafter.

In one embodiment of the invention, the compound of formula I

is a compound of any one of the following formulae I.1, 1.2, or 1.3.

In connection with compounds of formulae I.1, 1.2, or 1.3, it ispreferred that n is 0 or 1, i.e. that either R² is absent or only one R²is present.

It is to be understood that, depending on the synthesis of the compoundof formula I, also a mixture of, e.g., a compound of formula I.1. and acompound of formula I.3 may be present due to tautomerization before thestep of introducing the N-substituent R^(N). Therefore, the compound offormula I may in certain embodiments also be present as a mixture of acompound of formula I.1 and a compound of formula I.3. Furthermore,mixtures of formula I.2 compounds may be obtained, if at least onesubstituent R² is present.

Further, it is to be understood that depending on the presence orabsence of the substituent R² and its position, different structures maybe preferred in connection with the compounds of formula I.

Accordingly, the compound of formula I, in particular the compound offormula I.1, is in one particularly preferred embodiment a compound ofany one of formulae I.1(i), I.1(i), or I.1(iii) as depicted below.

In another particularly preferred embodiment, the compound of formula I,in particular the compound of formula I.2, is a compound of any one offormulae I.2(i), 1.2(ii), or 1.2(iii) as depicted below.

In another particularly preferred embodiment, the compound of formula I,in particular the compound of formula I.3, is a compound of any one offormulae I.3(i), 1.3(ii), or 1.3(iii) as depicted below.

In another preferred embodiment of the invention, in the compound offormula I, and preferably in the compounds of formulae I.1, 1.2, or 1.3,and in particular in the compounds of formulae I.1(i), I.1(ii), or1.1(iii), or in the compounds of formulae I.2(i), 1.2(ii), or 1.2(iii),or in the compounds of formulae I.3(i), 1.3(ii), or 1.3(iii),

-   R¹ is H, C₁-C₆-alkyl, C₃-C₆-cycloalkyl, benzyl, allyl,    CHR^(a)C(═O)OR^(b), CHR^(a)C(═O)NR^(b)R^(c) or phenyl, wherein said    phenyl group is unsubstituted or substituted by one or more, same or    different substituents R^(x);-   and-   R² if present, is halogen, C₁-C₆-alkyl, C₃-C₆-cycloalkyl, benzyl,    allyl, propargyl, or phenyl, wherein said phenyl group is    unsubstituted or substituted by one or more, same or different    substituents R^(x);-   wherein-   R^(a), R^(b), R^(c), and R^(x) are as defined above;-   and especially preferably-   R¹ is C₁-C₆-alkyl, benzyl, allyl; and-   R² if present, is C₁-C₃-alkyl or phenyl.

In connection with the above preferred embodiment, the meaning of R^(N)corresponds to the meaning provided above in connection with thecompounds of formula I.

Thus, in connection with the compounds of formulae I.1, 1.2, or 1.3 asdefined above, it is particularly preferred that R², if present, isC₁-C₃-alkyl or phenyl, and R¹ is C₁-C₆-alkyl, benzyl, allyl.

According to one preferred embodiment of the invention, the compound offormula I is a compound of formulae I.1, wherein n is 0 or 1, and R², ifpresent, is C₁-C₃-alkyl or phenyl, and R¹ is C₁-C₆-alkyl, benzyl, allyl.

According to one preferred embodiment of the invention, the compound offormula I is a compound of formulae I.2, wherein n is 0 or 1, and R², ifpresent, is C₁-C₃-alkyl or phenyl, and R¹ is C₁-C₆-alkyl, benzyl, allyl.

According to one preferred embodiment of the invention, the compound offormula I is a compound of formulae I.3, wherein n is 0 or 1, and R², ifpresent, is C₁-C₃-alkyl or phenyl, and R¹ is C₁-C₆-alkyl, benzyl, allyl.

In connection with the above preferred embodiments, the meaning of R^(N)corresponds to the meaning provided above in connection with thecompounds of formula I.

According to one particularly preferred embodiment, the compound offormula I is a compound of formula I.1(i), wherein R¹ is C₁-C₆-alkyl,benzyl, allyl.

According to one particularly preferred embodiment, the compound offormula I is a compound of formula I.1(ii), wherein R² is C₁-C₃-alkyl orphenyl, and wherein R¹ is C₁-C₆-alkyl, benzyl, allyl.

According to one particularly preferred embodiment, the compound offormula I is a compound of formula I.1(iii), wherein R² is C₁-C₃-alkylor phenyl, and wherein R¹ is C₁-C₆-alkyl, benzyl, allyl.

According to one particularly preferred embodiment, the compound offormula I is a compound of formula I.2(i), wherein R¹ is C₁-C₆-alkyl,benzyl, allyl.

According to one particularly preferred embodiment, the compound offormula I is a compound of formula I.2(ii), wherein R² is C₁-C₃-alkyl orphenyl, and wherein R¹ is C₁-C₆-alkyl, benzyl, allyl.

According to one particularly preferred embodiment, the compound offormula I is a compound of formula I.2(iii), wherein R² is C₁-C₃-alkylor phenyl, and wherein R¹ is C₁-C₆-alkyl, benzyl, allyl.

According to one particularly preferred embodiment, the compound offormula I is a compound of formula I.3(i), wherein R¹ is C₁-C₆-alkyl,benzyl, allyl.

According to one particularly preferred embodiment, the compound offormula I is a compound of formula I.3(ii), wherein R² is C₁-C₃-alkyl orphenyl, and wherein R¹ is C₁-C₆-alkyl, benzyl, allyl.

According to one particularly preferred embodiment, the compound offormula I is a compound of formula I.3(iii), wherein R² is C₁-C₃-alkylor phenyl, and wherein R¹ is C₁-C₆-alkyl, benzyl, allyl.

In connection with the above particularly preferred embodiments, themeaning of R^(N) corresponds to the meaning provided above in connectionwith the compounds of formula I.

In another embodiment of the invention, in the compound of formula I,and preferably in the compounds of formulae I.1, 1.2, or 1.3, andparticularly in the compounds of formulae I.1(i), I.1(i), or I.1(iii),or in the compounds of formulae I.2.(i), 1.2(ii), or I.2(iii), or in thecompounds of formulae I.3(i), 1.3(ii), or I.3(iii),

-   R^(N) is C₁-C₆-akyl C₃-C₆-cycloalkyl, benzyl, allyl, propargyl, or    phenyl, wherein said groups are unsubstituted or substituted by one    or more, same or different substituents R^(y); CHR^(a)C(═O)OR^(b),    CHR^(a)C(═O)NR^(b)R^(c), CH(C(═O)OR^(b))CH₂(C(═O)OR^(b));    C(═O)R^(d), C(═O)OR^(b), C(═O)NR^(b)R^(c), CHR^(a)OR^(b), or    CHR^(a)NR^(e)(C═O)R^(f);-   wherein-   R^(a) is H, C₁-C₄-alkyl, C₁-C₄-haloalkyl, C₃-C₈-cycloalkyl, phenyl,    or phenyl-C₁-C₂-alkyl;-   R^(b) is H, C₁-C₄-alkyl, C₁-C₄-haloalkyl, C₃-C₈-cycloalkyl, phenyl,    or phenyl-C₁-C₂-alkyl;-   R^(c) is H, C₁-C₄-alkyl, C₁-C₄-haloalkyl, or phenyl;-   R^(d) is H, C₁-C₈-alkyl, C₂-C₈-alkenyl, C₂-C₈-alkynyl, phenyl, or    phenyl-C₁-C₂-alkyl, wherein these groups are unsubstituted or    substituted by a group COOH;-   R^(e) is H, C₁-C₄-alkyl, C₃-C₈-cycloalkyl, or C₆-C₁₀-aryl;-   R^(f) is H, or C₁-C₄-alkyl;-   R^(y) is halogen, CN, OH, NO₂, COOH, NR^(b)R^(c), NR(C═O)R,    C(═O)NR^(b)R^(c), C₁-C₄-alkyl, C₁-C₄-haloalkyl, C₁-C₄-alkoxy,    C₁-C₄-haloalkoxy, C₁-C₄-alkylcarbonyl, C₁-C₄-alkylcarboxy,    C₁-C₄-alkylthio, C₁-C₄-alkylsulfonyl, and S(O)₂NR^(b)R^(c);-   and preferably-   R^(N) is C₁-C₆-akyl C₃-C₆-cycloalkyl, benzyl, allyl, propargyl, or    phenyl, wherein said groups are unsubstituted or substituted by one    or more, same or different substituents R^(Y);    -   CHR^(a)C(═O)OR, CHR^(a)C(═O)NR^(b)R^(c),        CH(C(═O)OR^(b))CH₂(C(═O)OR^(b));    -   C(═O)R^(d), C(═O)OR^(b), C(═O)NR^(b)R^(c), CHR^(a)OR^(b), or        CHR^(a)NR^(c)(C═O)R^(f);-   wherein-   R^(a) is H, C₁-C₄-alkyl, C₁-C₄-haloalkyl, C₃-C₈-cycloalkyl, phenyl,    or phenyl-C₁-C₂-alkyl;-   R^(b) is H, C₁-C₄-alkyl, C₁-C₄-haloalkyl, C₃-C₈-cycloalkyl, phenyl,    or phenyl-C₁-C₂-alkyl;-   R^(c) is H, C₁-C₄-alkyl, C₁-C₄-haloalkyl, or phenyl;-   R^(d) is H, or C₁-C₄-alkyl;-   R^(e) is H, or C₁-C₄-alkyl;-   R^(f) is H, or C₁-C₄-alkyl;-   R^(y) is halogen, CN, OH, NO₂, C₁-C₄-alkyl, C₁-C₄-haloalkyl,    C₁-C₄-alkoxy, and C₁-C₄-haloalkoxy;-   and especially preferably-   R^(N) is C(═O)R^(d), CHR^(a)C(═O)OR^(b), CHR^(a)C(═O)NR^(b)R^(c),    CH(C(═O)OR^(b))CH₂(C(═O)OR^(b)), or CHR^(a)NR^(c)(C═O) R;-   wherein-   R^(a) is H;-   R^(b) is H or C₁-C₄-alkyl;-   R^(c) is H or C₁-C₄-alkyl;-   R^(d) is C₁-C₃-alkyl;-   R^(e) is H;-   R^(f) is H or CH₃.

In one preferred embodiment of the invention, in the compound of formulaI

-   R^(N) is C(═O)R^(d), wherein preferably R^(d) is C₁-C₃-akyl Such    compounds are referred to as compounds of formula I.A.

In another preferred embodiment of the invention, in the compound offormula I R^(N) is CHR^(a)C(═O)OR^(b), wherein preferably R^(a) is H,and R^(b) is H or C₁-C₄-alkyl.

Such compounds are referred to as compounds of formula I.B.

In another preferred embodiment of the invention, in the compound offormula I R^(N) is CHR^(a)C(═O)NR^(b)R^(c), wherein preferably R^(a) isH, and R⁰ is H or C₁-C₄-alkyl, and R^(c) is H or C₁-C₄-alkyl.

Such compounds are referred to as compounds of formula I.C.

In another preferred embodiment of the invention, in the compound offormula I R^(N) is CH(C(═O)OR^(b))CH₂(C(═O)OR^(b)), wherein preferablyR⁰ is H or C₁-C₄-alkyl. In this connection, the two R^(b) substituentsmay be identical or different from each other.

Such compounds are referred to as compounds of formula I.D.

In another preferred embodiment of the invention, in the compound offormula I R^(N) is CHR^(a)NR^(c)(C═O)R^(f), wherein preferably R^(a) isH, and R^(c) is H, and R^(f) is H or CH₃.

Such compounds are referred to as compounds of formula I.E.

It is to be understood that the above preferences with regard to R¹ andR² also apply to the above formulae I.A, I.B, I.C, I.D and I.E.

Thus, particularly preferred compounds for use according to theinvention are compounds of formula I.1.A, I.1.B, I.1.C, I.1.D or I.1.E,which are depicted below.

The meanings of R¹ and R² preferably correspond to the meanings providedabove in connection with the compounds of formula I, in particular thecompounds of formula I.1. Furthermore, it is preferred that n is 0 or 1.If n is 1, each of the positions at the pyrazole ring may be realized byR² as indicated in connection with the compounds of formulae I.1(ii), orI.1(iii). Moreover, the meanings of R^(a), R^(b), R^(c), R^(d), R^(e),and R^(f) preferably correspond to the meanings provided above inconnection with the compounds of formulae I.A, I.B, I.C, I.D, and I.E.It is to be understood that if two substituents R^(b) are present, theymay be identical or different from each other.

Further, particularly preferred compounds for use according to theinvention are compounds of formula I.2.A, I.2.B, I.2.C, I.2.D or I.2.E,which are depicted below.

The meanings of R¹ and R² preferably correspond to the meanings providedabove in connection with the compounds of formula I, in particular thecompounds of formula I.2.

Furthermore, it is preferred that n is 0 or 1. If n is 1, each of thepositions at the pyrazole ring may be realized by R² as indicated inconnection with the compounds of formulae I.2(ii), or I.2(iii).Moreover, the meanings of R^(a), R^(b), R^(c), R^(d), R^(e), and Rpreferably correspond to the meanings provided above in connection withthe compounds of formulae I.A, I.B, I.C, ID, and I.E. It is to beunderstood that if two substituents R^(b) are present, they may beidentical or different from each other.

Further, particularly preferred compounds for use according to theinvention are compounds of formula I.3.A, 1.3.B, 1.3.C, I.3.D or I.3.E,which are depicted below.

The meanings of R¹ and R² preferably correspond to the meanings providedabove in connection with the compounds of formula I, in particular thecompounds of formula I.3. Furthermore, it is preferred that n is 0 or 1.If n is 1, each of the positions at the pyrazole ring may be realized byR² as indicated in connection with the compounds of formulae I.3(ii), orI.3(iii). Moreover, the meanings of R^(a), R^(b), R^(c), R^(d), R^(e),and R^(f) preferably correspond to the meanings provided above inconnection with the compounds of formulae I.A, I.B, I.C, I.D, and I.E.It is to be understood that if two substituents R^(b) are present, theymay be identical or different from each other.

Thus, particularly preferred compounds of formula I, in particularcompounds of formula I.1, I.2, or I.3, are compiled in the embodimentsbelow.

Embodiment 1

Compounds of the formula I.1(i), in which R^(N) is C(═O)R^(d) andcorresponds in each case to one row of Table A(i)

Embodiment 2

Compounds of the formula I.2(i), in which R^(N) is C(═O)R^(d) andcorresponds in each case to one row of Table A(i)

Embodiment 3

Compounds of the formula I.3(i), in which R^(N) is C(═O)R^(d) andcorresponds in each case to one row of Table A(i)

TABLE A(i) No. R^(N) (C(═O)R^(d)) A(i)-1 C(═O)CH₃ A(i)-2 C(═O)CH₂CH₃A(i)-3 C(═O)CH₂CH₂CH₃ A(i)-4 C(═O)CH(CH₃)₂

The meaning of R¹ in in connection with embodiments 1 to 3 preferablycorresponds to the meaning provided above in connection with thecompounds of formula I, in particular the compounds of formula I.1, I.2,or I.3.

Embodiment 4

Compounds of the formula I.1(i), in which R^(N) is CHR^(a)C(═O)OR^(b)and corresponds in each case to one row of Table A(ii)

Embodiment 5

Compounds of the formula I.2(i), in which R^(N) is CHR^(a)C(═O)OR^(b)and corresponds in each case to one row of Table A(ii)

Embodiment 6

Compounds of the formula I.3(i), in which R^(N) is CHR^(a)C(═O)OR^(b)and corresponds in each case to one row of Table A(ii)

TABLE A(ii) No. R^(N) (CHR^(a)C(═O)OR^(b)) A(ii)-1 CH₂C(═O)OH A(ii)-2CH₂C(═O)OCH₃ A(ii)-3 CH₂C(═O)OCH₂CH₃ A(ii)-4 CH₂C(═O)OCH₂CH₂CH₃ A(ii)-5CH₂C(═O)OCH(CH₃)₂

The meaning of R¹ in connection with embodiments 4 to 6 preferablycorresponds to the meaning provided above in connection with thecompounds of formula I, in particular the compounds of formula I.1, 1.2,or 1.3.

Embodiment 7

Compounds of the formula I.1(i), in which R^(N) isCHR^(a)C(═O)NR^(b)R^(c) and corresponds in each case to one row of TableA(iii)

Embodiment 8

Compounds of the formula I.2(i), in which R^(N) isCHR^(a)C(═O)NR^(b)R^(c) and corresponds in each case to one row of TableA(iii)

Embodiment 9

Compounds of the formula I.3(i), in which R^(N) isCHR^(a)C(═O)NR^(b)R^(c) and corresponds in each case to one row of TableA(iii)

TABLE A(iii) No. R^(N) (CHR^(a)C(═O)NR^(b)R^(c)) A(iii)-1 CH₂C(═O)NH₂A(iii)-2 CH₂C(═O)NHCH₃ A(iii)-3 CH₂C(═O)NH(CH₂CH₃) A(iii)-4CH₂C(═O)NH(CH₂CH₂CH₃) A(iii)-5 CH₂C(═O)NH(CH(CH₃)₂) A(iii)-6CH₂C(═O)N(CH₃)₂ A(iii)-7 CH₂C(═O)N(CH₂CH₃)CH₃ A(iii)-8CH₂C(═O)N(CH₂CH₂CH₃)CH₃ A(iii)-9 CH₂C(═O)N(CH(CH₃)₂)CH₃ A(iii)-10CH₂C(═O)N(CH₂CH₃)₂ A(iii)-11 CH₂C(═O)N(CH₂CH₂CH₃)(CH₂CH₃) A(iii)-12CH₂C(═O)N(CH(CH₃)₂)(CH₂CH₃) A(iii)-13 CH₂C(═O)N(CH₂CH₂CH₃)₂ A(iii)-14CH₂C(═O)N(CH(CH₃)₂)₂ A(iii)-15 CH₂C(═O)N(CH(CH₃)₂)(CH₂CH₂CH₃)

The meaning of R¹ in connection with embodiments 7 to 9 preferablycorresponds to the meaning provided above in connection with thecompounds of formula I, in particular the compounds of formula I.1, I.2,or I.3.

Embodiment 10

Compounds of the formula I.1(i), in which R^(N) isCH(C(═O)OR^(b))CH₂(C(═O)OR^(b)) and corresponds in each case to one rowof Table A(iv)

Embodiment 11

Compounds of the formula I.2(i), in which R^(N) isCH(C(═O)OR^(b))CH₂(C(═O)OR^(b)) and corresponds in each case to one rowof Table A(iv)

Embodiment 12

Compounds of the formula I.3(i), in which R^(N) isCH(C(═O)OR^(b))CH₂(C(═O)OR^(b)) and corresponds in each case to one rowof Table A(iv)

TABLE A(iv) No. R^(N) (CH(C(═O)OR^(b))CH₂(C(═O)OR^(b))) A(iv)-1CH(C(═O)OH)CH₂(C(═O)OH) A(iv)-2 CH(C(═O)OCH₃)CH₂(C(═O)OH) A(iv)-3CH(C(═O)OCH₂CH₃)CH₂(C(═O)OH) A(iv)-4 CH(C(═O)OCH₂CH₂CH₃)CH₂(C(═O)OH)A(iv)-5 CH(C(═O)OCH(CH₃)₂)CH₂(C(═O)OH) A(iv)-6 CH(C(═O)OH)CH₂(C(═O)OCH₃)A(iv)-7 CH(C(═O)OH)CH₂(C(═O)OCH₂CH₃) A(iv)-8CH(C(═O)OH)CH₂(C(═O)OCH₂CH₂CH₃) A(iv)-9 CH(C(═O)OH)CH₂(C(═O)OCH(CH₃)₂)A(iv)-10 CH(C(═O)OCH₃)CH₂(C(═O)OCH₃) A(iv)-11CH(C(═O)OCH₃)CH₂(C(═O)OCH₂CH₃) A(iv)-12CH(C(═O)OCH₃)CH₂(C(═O)OCH₂CH₂CH₃) A(iv)-13CH(C(═O)OCH₃)CH₂(C(═O)OCH(CH₃)₂) A(iv)-14 CH(C(═O)OCH₂CH₃)CH₂(C(═O)OCH₃)A(iv)-15 CH(C(═O)OCH₂CH₃)CH₂(C(═O)OCH₂CH₃) A(iv)-16CH(C(═O)OCH₂CH₃)CH₂(C(═O)OCH₂CH₂CH₃) A(iv)-17CH(C(═O)OCH₂CH₃)CH₂(C(═O)OCH(CH₃)₂) A(iv)-18CH(C(═O)OCH₂CH₂CH₃)CH₂(C(═O)OCH₃) A(iv)-19CH(C(═O)OCH(CH₃)₂)CH₂(C(═O)OCH₃) A(iv)-20CH(C(═O)OCH₂CH₂CH₃)CH₂(C(═O)OCH₂CH₃) A(iv)-21CH(C(═O)OCH(CH₃)₂)CH₂(C(═O)OCH₂CH₃) A(iv)-22CH(C(═O)OCH₂CH₂CH₃)CH₂(C(═O)OCH₂CH₂CH₃) A(iv)-23CH(C(═O)OCH(CH₃)₂)CH₂(C(═O)OCH₂CH₂CH₃) A(iv)-24CH(C(═O)OCH₂CH₂CH₃)CH₂(C(═O)OCH(CH₃)₂) A(iv)-25CH(C(═O)OCH(CH₃)₂)CH₂(C(═O)OCH(CH₃)₂)

The meaning of R¹ in connection with embodiments 10 to 12 preferablycorresponds to the meaning provided above in connection with thecompounds of formula I, in particular the compounds of formula I.1, I.2,or I.3.

Embodiment 13

Compounds of the formula I.1(i), in which R^(N) isCHR^(a)NR^(e)(C═O)R^(f) and corresponds in each case to one row of TableA(v)

Embodiment 14

Compounds of the formula I.2(i), in which R^(N) isCHR^(a)NR^(e)(C═O)R^(f) and corresponds in each case to one row of TableA(v)

Embodiment 15

Compounds of the formula I.3(i), in which R^(N) isCHR^(a)NR^(e)(C═O)R^(f) and corresponds in each case to one row of TableA(v)

TABLE A(v) No. R^(N) (CHR^(a)NR^(e)(C═O)R^(f)) A(v)-1 CH₂NH(C═O)H A(v)-2CH₂NH(C═O)CH₃

The meaning of R¹ in connection with embodiments 13 to 15 preferablycorresponds to the meaning provided above in connection with thecompounds of formula I, in particular the compounds of formula I.1, I.2,or I.3.

In connection with the methods, uses, compositions, and mixtures of theinvention, and in particular with a view to their use, preference isgiven to the compounds of formula I compiled in the tables below.

Table 1

Compounds of the formula I.1(i), wherein R² is absent and thecombination of R^(N) (C(═O)R^(d)) and R¹ corresponds in each case to onerow of Table B

Table 2

Compounds of the formula I.2(i), wherein R² is absent and thecombination of R^(N) (C(═O)R^(d)) and R¹ corresponds in each case to onerow of Table B

Table 3

Compounds of the formula I.3(i), wherein R² is absent and thecombination of R^(N) (C(═O)R^(d)) and R¹ corresponds in each case to onerow of Table B

Table 4

Compounds of the formula I.1(ii), wherein R² is CH₃ and the combinationof R^(N) (C(═O)R^(d)) and R¹ corresponds in each case to one row ofTable B

Table 5

Compounds of the formula I.1(iii), wherein R² is CH₃ and the combinationof R^(N) (C(═O)R^(d)) and R¹ corresponds in each case to one row ofTable B

Table 6

Compounds of the formula I.2(ii), wherein R² is CH₃ and the combinationof R^(N) (C(═O)R^(d)) and R¹ corresponds in each case to one row ofTable B

Table 7

Compounds of the formula I.2(iii), wherein R² is CH₃ and the combinationof R^(N) (C(═O)R^(d)) and R¹ corresponds in each case to one row ofTable B

Table 8

Compounds of the formula I.3(ii), wherein R² is CH₃ and the combinationof R^(N) (C(═O)R^(d)) and R¹ corresponds in each case to one row ofTable B

Table 9

Compounds of the formula I.3(iii), wherein R² is CH₃ and the combinationof R^(N) (C(═O)R^(d)) and R¹ corresponds in each case to one row ofTable B

Table 10

Compounds of the formula I.1(ii), wherein R² is CH₂CH₃ and thecombination of R^(N) (C(═O)R^(d)) and R¹ corresponds in each case to onerow of Table B

Table 11

Compounds of the formula I.1(iii), wherein R² is CH₂CH₃ and thecombination of R^(N)(C(═O)R^(d)) and R¹ corresponds in each case to onerow of Table B

Table 12

Compounds of the formula I.2(ii), wherein R² is CH₂CH₃ and thecombination of R^(N) (C(═O)R^(d)) and R¹ corresponds in each case to onerow of Table B

Table 13

Compounds of the formula I.2(iii), wherein R² is CH₂CH₃ and thecombination of R^(N)(C(═O)R^(d)) and R¹ corresponds in each case to onerow of Table B

Table 14

Compounds of the formula I.3(ii), wherein R² is CH₂CH₃ and thecombination of R^(N) (C(═O)R^(d)) and R¹ corresponds in each case to onerow of Table B

Table 15

Compounds of the formula I.3(iii), wherein R² is CH₂CH₃ and thecombination of R^(N)(C(═O)R^(d)) and R¹ corresponds in each case to onerow of Table B

Table 16

Compounds of the formula I.1(ii), wherein R² is CH₂CH₂CH₃ and thecombination of R^(N)(C(═O)R^(d)) and R¹ corresponds in each case to onerow of Table B

Table 17

Compounds of the formula I.1(ii), wherein R² is CH(CH₃)₂ and thecombination of R^(N)(C(═O)R^(d)) and R¹ corresponds in each case to onerow of Table B

Table 18

Compounds of the formula I.1(iii), wherein R² is CH₂CH₂CH₃ and thecombination of R^(N)(C(═O)R^(d)) and R¹ corresponds in each case to onerow of Table B

Table 19

Compounds of the formula I.1(iii), wherein R² is CH(CH₃)₂ and thecombination of R^(N)(C(═O)R^(d)) and R¹ corresponds in each case to onerow of Table B

Table 20

Compounds of the formula I.2(ii), wherein R² is CH₂CH₂CH₃ and thecombination of R^(N)(C(═O)R^(d)) and R¹ corresponds in each case to onerow of Table B

Table 21

Compounds of the formula I.2(ii), wherein R² is CH(CH₃)₂ and thecombination of R^(N)(C(═O)R^(d)) and R¹ corresponds in each case to onerow of Table B

Table 22

Compounds of the formula I.2(iii), wherein R² is CH₂CH₂CH₃ and thecombination of R^(N)(C(═O)R^(d)) and R¹ corresponds in each case to onerow of Table B

Table 23

Compounds of the formula I.2(iii), wherein R² is CH(CH₃)₂ and thecombination of R^(N)(C(═O)R^(d)) and R¹ corresponds in each case to onerow of Table B

Table 24

Compounds of the formula I.3(ii), wherein R² is CH₂CH₂CH₃ and thecombination of R^(N)(C(═O)R^(d)) and R¹ corresponds in each case to onerow of Table B

Table 25

Compounds of the formula I.3(ii), wherein R² is CH(CH₃)₂ and thecombination of R^(N)(C(═O)R^(d)) and R¹ corresponds in each case to onerow of Table B

Table 26

Compounds of the formula I.3(iii), wherein R² is CH₂CH₂CH₃ and thecombination of R^(N)(C(═O)R^(d)) and R¹ corresponds in each case to onerow of Table B

Table 27

Compounds of the formula I.3(iii), wherein R² is CH(CH₃)₂ and thecombination of R^(N)(C(═O)R^(d)) and R¹ corresponds in each case to onerow of Table B

Table 28

Compounds of the formula I.1(ii), wherein R² is phenyl and thecombination of R^(N) (C(═O)R¹) and R¹ corresponds in each case to onerow of Table B

Table 29

Compounds of the formula I.1(iii), wherein R² is phenyl and thecombination of R^(N) (C(═O)R^(d)) and R¹ corresponds in each case to onerow of Table B

Table 30

Compounds of the formula I.2(ii), wherein R² is phenyl and thecombination of R^(N) (C(═O)R¹) and R¹ corresponds in each case to onerow of Table B

Table 31

Compounds of the formula I.2(iii), wherein R² is phenyl and thecombination of R^(N) (C(═O)R^(d)) and R¹ corresponds in each case to onerow of Table B

Table 32

Compounds of the formula I.3(ii), wherein R² is phenyl and thecombination of R^(N) (C(═O)R¹) and R¹ corresponds in each case to onerow of Table B

Table 33

Compounds of the formula I.3(iii), wherein R² is phenyl and thecombination of R^(N) (C(═O)R^(d)) and R¹ corresponds in each case to onerow of Table B

TABLE B No. R¹ R^(N) (C(═O)R^(d)) B-1 CH₃ C(═O)CH₃ B-2 CH₂CH₃ C(═O)CH₃B-3 CH₂CH₂CH₃ C(═O)CH₃ B-4 CH(CH₃)₂ C(═O)CH₃ B-5 benzyl C(═O)CH₃ B-6allyl C(═O)CH₃ B-7 CH₃ C(═O)CH₂CH₃ B-8 CH₂CH₃ C(═O)CH₂CH₃ B-9 CH₂CH₂CH₃C(═O)CH₂CH₃ B-10 CH(CH₃)₂ C(═O)CH₂CH₃ B-11 benzyl C(═O)CH₂CH₃ B-12 allylC(═O)CH₂CH₃ B-13 CH₃ C(═O)CH₂CH₂CH₃ B-14 CH₂CH₃ C(═O)CH₂CH₂CH₃ B-15CH₂CH₂CH₃ C(═O)CH₂CH₂CH₃ B-16 CH(CH₃)₂ C(═O)CH₂CH₂CH₃ B-17 benzylC(═O)CH₂CH₂CH₃ B-18 allyl C(═O)CH₂CH₂CH₃ B-19 CH₃ C(═O)CH(CH₃)₂ B-20CH₂CH₃ C(═O)CH(CH₃)₂ B-21 CH₂CH₂CH₃ C(═O)CH(CH₃)₂ B-22 CH(CH₃)₂C(═O)CH(CH₃)₂ B-23 benzyl C(═O)CH(CH₃)₂ B-24 allyl C(═O)CH(CH₃)₂

Table 34

Compounds of the formula I.1(i), wherein R² is absent and thecombination of R^(N)(CHR^(a)C(═O)OR^(b)) and R¹ corresponds in each caseto one row of Table C

Table 35

Compounds of the formula I.2(i), wherein R² is absent and thecombination of R^(N)(CHR^(a)C(═O)OR^(b)) and R¹ corresponds in each caseto one row of Table C

Table 36

Compounds of the formula I.3(i), wherein R² is absent and thecombination of R^(N)(CHR^(a)C(═O)OR^(b)) and R¹ corresponds in each caseto one row of Table C

Table 37

Compounds of the formula I.1(ii), wherein R² is CH₃ and the combinationof R^(N)(CHR^(a)C(═O)OR^(b)) and R¹ corresponds in each case to one rowof Table C

Table 38

Compounds of the formula I.1(iii), wherein R² is CH₃ and the combinationof R^(N)(CHR^(a)C(═O)OR^(b)) and R¹ corresponds in each case to one rowof Table C

Table 39

Compounds of the formula I.2(ii), wherein R² is CH₃ and the combinationof R^(N)(CHR^(a)C(═O)OR^(b)) and R¹ corresponds in each case to one rowof Table C

Table 40

Compounds of the formula I.2(iii), wherein R² is CH₃ and the combinationof R^(N)(CHR^(a)C(═O)OR^(b)) and R¹ corresponds in each case to one rowof Table C

Table 41

Compounds of the formula I.3(ii), wherein R² is CH₃ and the combinationof R^(N)(CHR^(a)C(═O)OR^(b)) and R¹ corresponds in each case to one rowof Table C

Table 42

Compounds of the formula I.3(iii), wherein R² is CH₃ and the combinationof R^(N)(CHR^(a)C(═O)OR^(b)) and R¹ corresponds in each case to one rowof Table C

Table 43

Compounds of the formula I.1(ii), wherein R² is CH₂CH₃ and thecombination of R^(N)(CHR^(a)C(═O)OR^(b)) and R¹ corresponds in each caseto one row of Table C

Table 44

Compounds of the formula I.1(iii), wherein R² is CH₂CH₃ and thecombination of R^(N)(CHR^(a)C(═O)OR^(b)) and R¹ corresponds in each caseto one row of Table C

Table 45

Compounds of the formula I.2(ii), wherein R² is CH₂CH₃ and thecombination of R^(N)(CHR^(a)C(═O)OR^(b)) and R¹ corresponds in each caseto one row of Table C

Table 46

Compounds of the formula I.2(iii), wherein R² is CH₂CH₃ and thecombination of R^(N)(CHR^(a)C(═O)OR^(b)) and R¹ corresponds in each caseto one row of Table C

Table 47

Compounds of the formula I.3(ii), wherein R² is CH₂CH₃ and thecombination of R^(N)(CHR^(a)C(═O)OR^(b)) and R¹ corresponds in each caseto one row of Table C

Table 48

Compounds of the formula I.3(iii), wherein R² is CH₂CH₃ and thecombination of R^(N)(CHR^(a)C(═O)OR^(b)) and R¹ corresponds in each caseto one row of Table C

Table 49

Compounds of the formula I.1(ii), wherein R² is CH₂CH₂CH₃ and thecombination of R^(N)(CHR^(a)C(═O)OR^(b)) and R¹ corresponds in each caseto one row of Table C

Table 50

Compounds of the formula I.1(ii), wherein R² is CH(CH₃)₂ and thecombination of R^(N)(CHR^(a)C(═O)OR^(b)) and R¹ corresponds in each caseto one row of Table C

Table 51

Compounds of the formula I.1(iii), wherein R² is CH₂CH₂CH₃ and thecombination of R^(N)(CHR^(a)C(═O)OR^(b)) and R¹ corresponds in each caseto one row of Table C

Table 52

Compounds of the formula I.1(iii), wherein R² is CH(CH₃)₂ and thecombination of R^(N)(CHR^(a)C(═O)OR^(b)) and R¹ corresponds in each caseto one row of Table C

Table 53

Compounds of the formula I.2(ii), wherein R² is CH₂CH₂CH₃ and thecombination of R^(N)(CHR^(a)C(═O)OR^(b)) and R¹ corresponds in each caseto one row of Table C

Table 54

Compounds of the formula I.2(ii), wherein R² is CH(CH₃)₂ and thecombination of R^(N)(CHR^(a)C(═O)OR^(b)) and R¹ corresponds in each caseto one row of Table C

Table 55

Compounds of the formula I.2(iii), wherein R² is CH₂CH₂CH₃ and thecombination of R^(N)(CHR^(a)C(═O)OR^(b)) and R¹ corresponds in each caseto one row of Table C

Table 56

Compounds of the formula I.2(iii), wherein R² is CH(CH₃)₂ and thecombination of R^(N)(CHR^(a)C(═O)OR^(b)) and R¹ corresponds in each caseto one row of Table C

Table 57

Compounds of the formula I.3(ii), wherein R² is CH₂CH₂CH₃ and thecombination of R^(N)(CHR^(a)C(═O)OR^(b)) and R¹ corresponds in each caseto one row of Table C

Table 58

Compounds of the formula I.3(ii), wherein R² is CH(CH₃)₂ and thecombination of R^(N)(CHR^(a)C(═O)OR^(b)) and R¹ corresponds in each caseto one row of Table C

Table 59

Compounds of the formula I.3(iii), wherein R² is CH₂CH₂CH₃ and thecombination of R^(N)(CHR^(a)C(═O)OR^(b)) and R¹ corresponds in each caseto one row of Table C

Table 60

Compounds of the formula I.3(iii), wherein R² is CH(CH₃)₂ and thecombination of R^(N)(CHR^(a)C(═O)OR^(b)) and R¹ corresponds in each caseto one row of Table C

Table 61

Compounds of the formula I.1(ii), wherein R² is phenyl and thecombination of R^(N)(CHR^(a)C(═O)OR^(b)) and R¹ corresponds in each caseto one row of Table C

Table 62

Compounds of the formula I.1(iii), wherein R² is phenyl and thecombination of R^(N)(CHR^(a)C(═O)OR^(b)) and R¹ corresponds in each caseto one row of Table C

Table 63

Compounds of the formula I.2(ii), wherein R² is phenyl and thecombination of R^(N)(CHR^(a)C(═O)OR^(b)) and R¹ corresponds in each caseto one row of Table C

Table 64

Compounds of the formula I.2(iii), wherein R² is phenyl and thecombination of R^(N)(CHR^(a)C(═O)OR^(b)) and R¹ corresponds in each caseto one row of Table C

Table 65

Compounds of the formula I.3(ii), wherein R² is phenyl and thecombination of R^(N)(CHR^(a)C(═O)OR^(b)) and R¹ corresponds in each caseto one row of Table C

Table 66

Compounds of the formula I.3(iii), wherein R² is phenyl and thecombination of R^(N) (CHR^(a)C(═O)OR^(b)) and R¹ corresponds in eachcase to one row of Table C

TABLE C No. R¹ R^(N) (CHR^(a)C(═O)OR^(b)) C-1 CH₃ CH₂C(═O)OH C-2 CH₂CH₃CH₂C(═O)OH C-3 CH₂CH₂CH₃ CH₂C(═O)OH C-4 CH(CH₃)₂ CH₂C(═O)OH C-5 benzylCH₂C(═O)OH C-6 allyl CH₂C(═O)OH C-7 CH₃ CH₂C(═O)OCH₃ C-8 CH₂CH₃CH₂C(═O)OCH₃ C-9 CH₂CH₂CH₃ CH₂C(═O)OCH₃ C-10 CH(CH₃)₂ CH₂C(═O)OCH₃ C-11benzyl CH₂C(═O)OCH₃ C-12 allyl CH₂C(═O)OCH₃ C-13 CH₃ CH₂C(═O)OCH₂CH₃C-14 CH₂CH₃ CH₂C(═O)OCH₂CH₃ C-15 CH₂CH₂CH₃ CH₂C(═O)OCH₂CH₃ C-16 CH(CH₃)₂CH₂C(═O)OCH₂CH₃ C-17 benzyl CH₂C(═O)OCH₂CH₃ C-18 allyl CH₂C(═O)OCH₂CH₃C-19 CH₃ CH₂C(═O)OCH₂CH₂CH₃ C-20 CH₂CH₃ CH₂C(═O)OCH₂CH₂CH₃ C-21CH₂CH₂CH₃ CH₂C(═O)OCH₂CH₂CH₃ C-22 CH(CH₃)₂ CH₂C(═O)OCH₂CH₂CH₃ C-23benzyl CH₂C(═O)OCH₂CH₂CH₃ C-24 allyl CH₂C(═O)OCH₂CH₂CH₃ C-25 CH₃CH₂C(═O)OCH(CH₃)₂ C-26 CH₂CH₃ CH₂C(═O)OCH(CH₃)₂ C-27 CH₂CH₂CH₃CH₂C(═O)OCH(CH₃)₂ C-28 CH(CH₃)₂ CH₂C(═O)OCH(CH₃)₂ C-29 benzylCH₂C(═O)OCH(CH₃)₂ C-30 allyl CH₂C(═O)OCH(CH₃)₂

Table 67

Compounds of the formula I.1(i), wherein R² is absent and thecombination of R^(N)(CHR^(a)C(═O)NR^(b)R^(c)) and R¹ corresponds in eachcase to one row of Table D

Table 68

Compounds of the formula I.2(i), wherein R² is absent and thecombination of R^(N)(CHR^(a)C(═O)NR^(b)R^(c)) and R¹ corresponds in eachcase to one row of Table D

Table 69

Compounds of the formula I.3(i), wherein R² is absent and thecombination of R^(N)(CHR^(a)C(═O)NR^(b)R^(c)) and R¹ corresponds in eachcase to one row of Table D

Table 70

Compounds of the formula I.1(ii), wherein R² is CH₃ and the combinationof R^(N)(CHR^(a)C(═O)NR^(b)R^(c)) and R¹ corresponds in each case to onerow of Table D

Table 71

Compounds of the formula I.1(iii), wherein R² is CH₃ and the combinationof R^(N)(CHR^(a)C(═O)NR^(b)R^(c)) and R¹ corresponds in each case to onerow of Table D

Table 72

Compounds of the formula I.2(ii), wherein R² is CH₃ and the combinationof R^(N)(CHR^(a)C(═O)NR^(b)R^(c)) and R¹ corresponds in each case to onerow of Table D

Table 73

Compounds of the formula I.2(iii), wherein R² is CH₃ and the combinationof R^(N)(CHR^(a)C(═O)NR^(b)R^(c)) and R¹ corresponds in each case to onerow of Table D

Table 74

Compounds of the formula I.3(ii), wherein R² is CH₃ and the combinationof R^(N)(CHR^(a)C(═O)NR^(b)R^(c)) and R¹ corresponds in each case to onerow of Table D

Table 75

Compounds of the formula I.3(iii), wherein R² is CH₃ and the combinationof R^(N)(CHR^(a)C(═O)NR^(b)R^(c)) and R¹ corresponds in each case to onerow of Table D

Table 76

Compounds of the formula I.1(ii), wherein R² is CH₂CH₃ and thecombination of R^(N)(CHR^(a)C(═O)NR^(b)R^(c)) and R¹ corresponds in eachcase to one row of Table D

Table 77

Compounds of the formula I.1(iii), wherein R² is CH₂CH₃ and thecombination of R^(N)(CHR^(a)C(═O)NR^(b)R^(c)) and R¹ corresponds in eachcase to one row of Table D

Table 78

Compounds of the formula I.2(ii), wherein R² is CH₂CH₃ and thecombination of R^(N)(CHR^(a)C(═O)NR^(b)R^(c)) and R¹ corresponds in eachcase to one row of Table D

Table 79

Compounds of the formula I.2(iii), wherein R² is CH₂CH₃ and thecombination of R^(N)(CHR^(a)C(═O)NR^(b)R^(c)) and R¹ corresponds in eachcase to one row of Table D

Table 80

Compounds of the formula I.3(ii), wherein R² is CH₂CH₃ and thecombination of R^(N)(CHR^(a)C(═O)NR^(b)R^(c)) and R¹ corresponds in eachcase to one row of Table D

Table 81

Compounds of the formula I.3(iii), wherein R² is CH₂CH₃ and thecombination of R^(N)(CHR^(a)C(═O)NR^(b)R^(c)) and R¹ corresponds in eachcase to one row of Table D

Table 82

Compounds of the formula I.1(ii), wherein R² is CH₂CH₂CH₃ and thecombination of R^(N)(CHR^(a)C(═O)NR^(b)R^(c)) and R¹ corresponds in eachcase to one row of Table D

Table 83

Compounds of the formula I.1(ii), wherein R² is CH(CH₃)₂ and thecombination of R^(N)(CHR^(a)C(═O)NR^(b)R^(c)) and R¹ corresponds in eachcase to one row of Table D

Table 84

Compounds of the formula I.1(iii), wherein R² is CH₂CH₂CH₃ and thecombination of R^(N)(CHR^(a)C(═O)NR^(b)R^(c)) and R¹ corresponds in eachcase to one row of Table D

Table 85

Compounds of the formula I.1(iii), wherein R² is CH(CH₃)₂ and thecombination of R^(N)(CHR^(a)C(═O)NR^(b)R^(c)) and R¹ corresponds in eachcase to one row of Table D

Table 86

Compounds of the formula I.2(ii), wherein R² is CH₂CH₂CH₃ and thecombination of R^(N)(CHR^(a)C(═O)NR^(b)R^(c)) and R¹ corresponds in eachcase to one row of Table D

Table 87

Compounds of the formula I.2(ii), wherein R² is CH(CH₃)₂ and thecombination of R^(N)(CHR^(a)C(═O)NR^(b)R^(c)) and R¹ corresponds in eachcase to one row of Table D

Table 88

Compounds of the formula I.2(iii), wherein R² is CH₂CH₂CH₃ and thecombination of R^(N)(CHR^(a)C(═O)NR^(b)R^(c)) and R¹ corresponds in eachcase to one row of Table D

Table 89

Compounds of the formula I.2(iii), wherein R² is CH(CH₃)₂ and thecombination of R^(N)(CHR^(a)C(═O)NR^(b)R^(c)) and R¹ corresponds in eachcase to one row of Table D

Table 90

Compounds of the formula I.3(ii), wherein R² is CH₂CH₂CH₃ and thecombination of R^(N)(CHR^(a)C(═O)NR^(b)R^(c)) and R¹ corresponds in eachcase to one row of Table D

Table 91

Compounds of the formula I.3(ii), wherein R² is CH(CH₃)₂ and thecombination of R^(N)(CHR^(a)C(═O)NR^(b)R^(c)) and R¹ corresponds in eachcase to one row of Table D

Table 92

Compounds of the formula I.3(iii), wherein R² is CH₂CH₂CH₃ and thecombination of R^(N)(CHR^(a)C(═O)NR^(b)R^(c)) and R¹ corresponds in eachcase to one row of Table D

Table 93

Compounds of the formula I.3(iii), wherein R² is CH(CH₃)₂ and thecombination of R^(N)(CHR^(a)C(═O)NR^(b)R^(c)) and R¹ corresponds in eachcase to one row of Table D

Table 94

Compounds of the formula I.1(ii), wherein R² is phenyl and thecombination of R^(N)(CHR^(a)C(═O)NR^(b)R^(c)) and R¹ corresponds in eachcase to one row of Table D

Table 95

Compounds of the formula I.1(iii), wherein R² is phenyl and thecombination of R^(N)(CHR^(a)C(═O)NR^(b)R^(c)) and R¹ corresponds in eachcase to one row of Table D

Table 96

Compounds of the formula I.2(ii), wherein R² is phenyl and thecombination of R^(N)(CHR^(a)C(═O)NR^(b)R^(c)) and R¹ corresponds in eachcase to one row of Table D

Table 97

Compounds of the formula I.2(iii), wherein R² is phenyl and thecombination of R^(N)(CHR^(a)C(═O)NR^(b)R^(c)) and R¹ corresponds in eachcase to one row of Table D

Table 98

Compounds of the formula I.3(ii), wherein R² is phenyl and thecombination of R^(N)(CHR^(a)C(═O)NR^(b)R^(c)) and R¹ corresponds in eachcase to one row of Table D

Table 99

Compounds of the formula I.3(iii), wherein R² is phenyl and thecombination of R^(N)(CHR^(a)C(═O)NR^(b)R^(c)) and R¹ corresponds in eachcase to one row of Table D Table D

TABLE D No. R¹ R^(N) (CHR^(a)C(═O)NR^(b)R^(c)) D-1 CH₃ CH₂C(═O)NH₂ D-2CH₂CH₃ CH₂C(═O)NH₂ D-3 CH₂CH₂CH₃ CH₂C(═O)NH₂ D-4 CH(CH₃)₂ CH₂C(═O)NH₂D-5 benzyl CH₂C(═O)NH₂ D-6 allyl CH₂C(═O)NH₂ D-7 CH₃ CH₂C(═O)NHCH₃ D-8CH₂CH₃ CH₂C(═O)NHCH₃ D-9 CH₂CH₂CH₃ CH₂C(═O)NHCH₃ D-10 CH(CH₃)₂CH₂C(═O)NHCH₃ D-11 benzyl CH₂C(═O)NHCH₃ D-12 allyl CH₂C(═O)NHCH₃ D-13CH₃ CH₂C(═O)NH(CH₂CH₃) D-14 CH₂CH₃ CH₂C(═O)NH(CH₂CH₃) D-15 CH₂CH₂CH₃CH₂C(═O)NH(CH₂CH₃) D-16 CH(CH₃)₂ CH₂C(═O)NH(CH₂CH₃) D-17 benzylCH₂C(═O)NH(CH₂CH₃) D-18 allyl CH₂C(═O)NH(CH₂CH₃) D-19 CH₃CH₂C(═O)NH(CH₂CH₂CH₃) D-20 CH₂CH₃ CH₂C(═O)NH(CH₂CH₂CH₃) D-21 CH₂CH₂CH₃CH₂C(═O)NH(CH₂CH₂CH₃) D-22 CH(CH₃)₂ CH₂C(═O)NH(CH₂CH₂CH₃) D-23 benzylCH₂C(═O)NH(CH₂CH₂CH₃) D-24 allyl CH₂C(═O)NH(CH₂CH₂CH₃) D-25 CH₃CH₂C(═O)NH(CH(CH₃)₂) D-26 CH₂CH₃ CH₂C(═O)NH(CH(CH₃)₂) D-27 CH₂CH₂CH₃CH₂C(═O)NH(CH(CH₃)₂) D-28 CH(CH₃)₂ CH₂C(═O)NH(CH(CH₃)₂) D-29 benzylCH₂C(═O)NH(CH(CH₃)₂) D-30 allyl CH₂C(═O)NH(CH(CH₃)₂) D-31 CH₃CH₂C(═O)N(CH₃)₂ D-32 CH₂CH₃ CH₂C(═O)N(CH₃)₂ D-33 CH₂CH₂CH₃CH₂C(═O)N(CH₃)₂ D-34 CH(CH₃)₂ CH₂C(═O)N(CH₃)₂ D-35 benzylCH₂C(═O)N(CH₃)₂ D-36 allyl CH₂C(═O)N(CH₃)₂ D-37 CH₃ CH₂C(═O)N(CH₂CH₃)CH₃D-38 CH₂CH₃ CH₂C(═O)N(CH₂CH₃)CH₃ D-39 CH₂CH₂CH₃ CH₂C(═O)N(CH₂CH₃)CH₃D-40 CH(CH₃)₂ CH₂C(═O)N(CH₂CH₃)CH₃ D-41 benzyl CH₂C(═O)N(CH₂CH₃)CH₃ D-42allyl CH₂C(═O)N(CH₂CH₃)CH₃ D-43 CH₃ CH₂C(═O)N(CH₂CH₂CH₃)CH₃ D-44 CH₂CH₃CH₂C(═O)N(CH₂CH₂CH₃)CH₃ D-45 CH₂CH₂CH₃ CH₂C(═O)N(CH₂CH₂CH₃)CH₃ D-46CH(CH₃)₂ CH₂C(═O)N(CH₂CH₂CH₃)CH₃ D-47 benzyl CH₂C(═O)N(CH₂CH₂CH₃)CH₃D-48 allyl CH₂C(═O)N(CH₂CH₂CH₃)CH₃ D-49 CH₃ CH₂C(═O)N(CH(CH₃)₂)CH₃ D-50CH₂CH₃ CH₂C(═O)N(CH(CH₃)₂)CH₃ D-51 CH₂CH₂CH₃ CH₂C(═O)N(CH(CH₃)₂)CH₃ D-52CH(CH₃)₂ CH₂C(═O)N(CH(CH₃)₂)CH₃ D-53 benzyl CH₂C(═O)N(CH(CH₃)₂)CH₃ D-54allyl CH₂C(═O)N(CH(CH₃)₂)CH₃ D-55 CH₃ CH₂C(═O)N(CH₂CH₃)₂ D-56 CH₂CH₃CH₂C(═O)N(CH₂CH₃)₂ D-57 CH₂CH₂CH₃ CH₂C(═O)N(CH₂CH₃)₂ D-58 CH(CH₃)₂CH₂C(═O)N(CH₂CH₃)₂ D-59 benzyl CH₂C(═O)N(CH₂CH₃)₂ D-60 allylCH₂C(═O)N(CH₂CH₃)₂ D-61 CH₃ CH₂C(═O)N(CH₂CH₂CH₃)(CH₂CH₃) D-62 CH₂CH₃CH₂C(═O)N(CH₂CH₂CH₃)(CH₂CH₃) D-63 CH₂CH₂CH₃ CH₂C(═O)N(CH₂CH₂CH₃)(CH₂CH₃)D-64 CH(CH₃)₂ CH₂C(═O)N(CH₂CH₂CH₃)(CH₂CH₃) D-65 benzylCH₂C(═O)N(CH₂CH₂CH₃)(CH₂CH₃) D-66 allyl CH₂C(═O)N(CH₂CH₂CH₃)(CH₂CH₃)D-67 CH₃ CH₂C(═O)N(CH(CH₃)₂)(CH₂CH₃) D-68 CH₂CH₃CH₂C(═O)N(CH(CH₃)₂)(CH₂CH₃) D-69 CH₂CH₂CH₃ CH₂C(═O)N(CH(CH₃)₂)(CH₂CH₃)D-70 CH(CH₃)₂ CH₂C(═O)N(CH(CH₃)₂)(CH₂CH₃) D-71 benzylCH₂C(═O)N(CH(CH₃)₂)(CH₂CH₃) D-72 allyl CH₂C(═O)N(CH(CH₃)₂)(CH₂CH₃) D-73CH₃ CH₂C(═O)N(CH₂CH₂CH₃)₂ D-74 CH₂CH₃ CH₂C(═O)N(CH₂CH₂CH₃)₂ D-75CH₂CH₂CH₃ CH₂C(═O)N(CH₂CH₂CH₃)₂ D-76 CH(CH₃)₂ CH₂C(═O)N(CH₂CH₂CH₃)₂ D-77benzyl CH₂C(═O)N(CH₂CH₂CH₃)₂ D-78 allyl CH₂C(═O)N(CH₂CH₂CH₃)₂ D-79 CH₃CH₂C(═O)N(CH(CH₃)₂)₂ D-80 CH₂CH₃ CH₂C(═O)N(CH(CH₃)₂)₂ D-81 CH₂CH₂CH₃CH₂C(═O)N(CH(CH₃)₂)₂ D-82 CH(CH₃)₂ CH₂C(═O)N(CH(CH₃)₂)₂ D-83 benzylCH₂C(═O)N(CH(CH₃)₂)₂ D-84 allyl CH₂C(═O)N(CH(CH₃)₂)₂ D-85 CH₃CH₂C(═O)N(CH(CH₃)₂)(CH₂CH₂CH₃) D-86 CH₂CH₃CH₂C(═O)N(CH(CH₃)₂)(CH₂CH₂CH₃) D-87 CH₂CH₂CH₃CH₂C(═O)N(CH(CH₃)₂)(CH₂CH₂CH₃) D-88 CH(CH₃)₂CH₂C(═O)N(CH(CH₃)₂)(CH₂CH₂CH₃) D-89 benzylCH₂C(═O)N(CH(CH₃)₂)(CH₂CH₂CH₃) D-90 allyl CH₂C(═O)N(CH(CH₃)₂)(CH₂CH₂CH₃)

Table 100

Compounds of the formula I.1(i), wherein R² is absent and thecombination of R^(N)(CH(C(═O)OR^(b))CH₂(C(═O)OR^(b))) and R¹ correspondsin each case to one row of Table E

Table 101

Compounds of the formula I.2(i), wherein R² is absent and thecombination of R^(N)(CH(C(═O)OR^(b))CH₂(C(═O)OR^(b))) and R¹ correspondsin each case to one row of Table E

Table 102

Compounds of the formula I.3(i), wherein R² is absent and thecombination of R^(N)(CH(C(═O)OR^(b))CH₂(C(═O)OR^(b))) and R¹ correspondsin each case to one row of Table E

Table 103

Compounds of the formula I.1(ii), wherein R² is CH₃ and the combinationof R^(N)(CH(C(═O)OR^(b))CH₂(C(═O)OR^(b))) and R¹ corresponds in eachcase to one row of Table E

Table 104

Compounds of the formula I.1(iii), wherein R² is CH₃ and the combinationof R^(N)(CH(C(═O)OR^(b))CH₂(C(═O)OR^(b))) and R¹ corresponds in eachcase to one row of Table E

Table 105

Compounds of the formula I.2(ii), wherein R² is CH₃ and the combinationof R^(N)(CH(C(═O)OR^(b))CH₂(C(═O)OR^(b))) and R¹ corresponds in eachcase to one row of Table E

Table 106

Compounds of the formula I.2(iii), wherein R² is CH₃ and the combinationof R^(N)(CH(C(═O)OR^(b))CH₂(C(═O)OR^(b))) and R¹ corresponds in eachcase to one row of Table E

Table 107

Compounds of the formula I.3(ii), wherein R² is CH₃ and the combinationof R^(N)(CH(C(═O)OR^(b))CH₂(C(═O)OR^(b))) and R¹ corresponds in eachcase to one row of Table E

Table 108

Compounds of the formula I.3(iii), wherein R² is CH₃ and the combinationof R^(N)(CH(C(═O)OR^(b))CH₂(C(═O)OR^(b))) and R¹ corresponds in eachcase to one row of Table E

Table 109

Compounds of the formula I.1(ii), wherein R² is CH₂CH₃ and thecombination of R^(N)(CH(C(═O)OR^(b))CH₂(C(═O)OR^(b))) and R¹ correspondsin each case to one row of Table E

Table 110

Compounds of the formula I.1(iii), wherein R² is CH₂CH₃ and thecombination of R^(N)(CH(C(═O)OR^(b))CH₂(C(═O)OR^(b))) and R¹ correspondsin each case to one row of Table E

Table 111

Compounds of the formula I.2(ii), wherein R² is CH₂CH₃ and thecombination of R^(N)(CH(C(═O)OR^(b))CH₂(C(═O)OR^(b))) and R¹ correspondsin each case to one row of Table E

Table 112

Compounds of the formula I.2(iii), wherein R² is CH₂CH₃ and thecombination of R^(N)(CH(C(═O)OR^(b))CH₂(C(═O)OR^(b))) and R¹ correspondsin each case to one row of Table E

Table 113

Compounds of the formula I.3(ii), wherein R² is CH₂CH₃ and thecombination of R^(N)(CH(C(═O)OR^(b))CH₂(C(═O)OR^(b))) and R¹ correspondsin each case to one row of Table E

Table 114

Compounds of the formula I.3(iii), wherein R² is CH₂CH₃ and thecombination of R^(N)(CH(C(═O)OR^(b))CH₂(C(═O)OR^(b))) and R¹ correspondsin each case to one row of Table E

Table 115

Compounds of the formula I.1(ii), wherein R² is CH₂CH₂CH₃ and thecombination of R^(N)(CH(C(═O)OR^(b))CH₂(C(═O)OR^(b))) and R¹ correspondsin each case to one row of Table E

Table 116

Compounds of the formula I.1(ii), wherein R² is CH(CH₃)₂ and thecombination of R^(N)(CH(C(═O)OR^(b))CH₂(C(═O)OR^(b))) and R¹ correspondsin each case to one row of Table E

Table 117

Compounds of the formula I.1(iii), wherein R² is CH₂CH₂CH₃ and thecombination of R^(N)(CH(C(═O)OR^(b))CH₂(C(═O)OR^(b))) and R¹ correspondsin each case to one row of Table E

Table 118

Compounds of the formula I.1(iii), wherein R² is CH(CH₃)₂ and thecombination of R^(N)(CH(C(═O)OR^(b))CH₂(C(═O)OR^(b))) and R¹ correspondsin each case to one row of Table E

Table 119

Compounds of the formula I.2(ii), wherein R² is CH₂CH₂CH₃ and thecombination of R^(N)(CH(C(═O)OR^(b))CH₂(C(═O)OR^(b))) and R¹ correspondsin each case to one row of Table E

Table 120

Compounds of the formula I.2(ii), wherein R² is CH(CH₃)₂ and thecombination of R^(N)(CH(C(═O)OR^(b))CH₂(C(═O)OR^(b))) and R¹ correspondsin each case to one row of Table E

Table 121

Compounds of the formula I.2(iii), wherein R² is CH₂CH₂CH₃ and thecombination of R^(N)(CH(C(═O)OR^(b))CH₂(C(═O)OR^(b))) and R¹ correspondsin each case to one row of Table E

Table 122

Compounds of the formula I.2(iii), wherein R² is CH(CH₃)₂ and thecombination of R^(N)(CH(C(═O)OR^(b))CH₂(C(═O)OR^(b))) and R¹ correspondsin each case to one row of Table E

Table 123

Compounds of the formula I.3(ii), wherein R² is CH₂CH₂CH₃ and thecombination of R^(N)(CH(C(═O)OR^(b))CH₂(C(═O)OR^(b))) and R¹ correspondsin each case to one row of Table E

Table 124

Compounds of the formula I.3(ii), wherein R² is CH(CH₃)₂ and thecombination of R^(N)(CH(C(═O)OR^(b))CH₂(C(═O)OR^(b))) and R¹ correspondsin each case to one row of Table E

Table 125

Compounds of the formula I.3(iii), wherein R² is CH₂CH₂CH₃ and thecombination of R^(N)(CH(C(═O)OR^(b))CH₂(C(═O)OR^(b))) and R¹ correspondsin each case to one row of Table E

Table 126

Compounds of the formula I.3(iii), wherein R² is CH(CH₃)₂ and thecombination of R^(N)(CH(C(═O)OR^(b))CH₂(C(═O)OR^(b))) and R¹ correspondsin each case to one row of Table E

Table 127

Compounds of the formula I.1(ii), wherein R² is phenyl and thecombination of R^(N)(CH(C(═O)OR^(b))CH₂(C(═O)OR^(b))) and R¹ correspondsin each case to one row of Table E

Table 128

Compounds of the formula I.1(iii), wherein R² is phenyl and thecombination of R^(N)(CH(C(═O)OR^(b))CH₂(C(═O)OR^(b))) and R¹ correspondsin each case to one row of Table E

Table 129

Compounds of the formula I.2(ii), wherein R² is phenyl and thecombination of R^(N)(CH(C(═O)OR^(b))CH₂(C(═O)OR^(b))) and R¹ correspondsin each case to one row of Table E

Table 130

Compounds of the formula I.2(iii), wherein R² is phenyl and thecombination of R^(N)(CH(C(═O)OR^(b))CH₂(C(═O)OR^(b))) and R^(N)corresponds in each case to one row of Tale E

Table 131

Compounds of the formula I.3(ii), wherein R² is phenyl and thecombination of R^(N)(CH(C(═O)OR^(b))CH₂(C(═O)OR^(b))) and C correspondsin each case to one row of Tale

Table 132

Compounds of the formula I.3(iii), wherein R² is phenyl and thecombination of R^(N)(CH(C(═O)OR^(b))CH₂(C(═O)OR^(b))) and R¹ correspondsin each case to one row of Table E

TABLE E No. R¹ R^(N) (CH(C(═O)OR^(b))CH₂(C(═O)OR^(b)) E-1 CH₃CH(C(═O)OH)CH₂(C(═O)OH) E-2 CH₂CH₃ CH(C(═O)OH)CH₂(C(═O)OH) E-3 CH₂CH₂CH₃CH(C(═O)OH)CH₂(C(═O)OH) E-4 CH(CH₃)₂ CH(C(═O)OH)CH₂(C(═O)OH) E-5 benzylCH(C(═O)OH)CH₂(C(═O)OH) E-6 allyl CH(C(═O)OH)CH₂(C(═O)OH) E-7 CH₃CH(C(═O)OCH₃)CH₂(C(═O)OH) E-8 CH₂CH₃ CH(C(═O)OCH₃)CH₂(C(═O)OH) E-9CH₂CH₂CH₃ CH(C(═O)OCH₃)CH₂(C(═O)OH) E-10 CH(CH₃)₂CH(C(═O)OCH₃)CH₂(C(═O)OH) E-11 benzyl CH(C(═O)OCH₃)CH₂(C(═O)OH) E-12allyl CH(C(═O)OCH₃)CH₂(C(═O)OH) E-13 CH₃ CH(C(═O)OCH₂CH₃)CH₂(C(═O)OH)E-14 CH₂CH₃ CH(C(═O)OCH₂CH₃)CH₂(C(═O)OH) E-15 CH₂CH₂CH₃CH(C(═O)OCH₂CH₃)CH₂(C(═O)OH) E-16 CH(CH₃)₂ CH(C(═O)OCH₂CH₃)CH₂(C(═O)OH)E-17 benzyl CH(C(═O)OCH₂CH₃)CH₂(C(═O)OH) E-18 allylCH(C(═O)OCH₂CH₃)CH₂(C(═O)OH) E-19 CH₃ CH(C(═O)OCH₂CH₂CH₃)CH₂(C(═O)OH)E-20 CH₂CH₃ CH(C(═O)OCH₂CH₂CH₃)CH₂(C(═O)OH) E-21 CH₂CH₂CH₃CH(C(═O)OCH₂CH₂CH₃)CH₂(C(═O)OH) E-22 CH(CH₃)₂CH(C(═O)OCH₂CH₂CH₃)CH₂(C(═O)OH) E-23 benzylCH(C(═O)OCH₂CH₂CH₃)CH₂(C(═O)OH) E-24 allylCH(C(═O)OCH₂CH₂CH₃)CH₂(C(═O)OH) E-25 CH₃ CH(C(═O)OCH(CH₃)₂)CH₂(C(═O)OH)E-26 CH₂CH₃ CH(C(═O)OCH(CH₃)₂)CH₂(C(═O)OH) E-27 CH₂CH₂CH₃CH(C(═O)OCH(CH₃)₂)CH₂(C(═O)OH) E-28 CH(CH₃)₂CH(C(═O)OCH(CH₃)₂)CH₂(C(═O)OH) E-29 benzylCH(C(═O)OCH(CH₃)₂)CH₂(C(═O)OH) E-30 allyl CH(C(═O)OCH(CH₃)₂)CH₂(C(═O)OH)E-31 CH₃ CH(C(═O)OH)CH₂(C(═O)OCH₃) E-32 CH₂CH₃ CH(C(═O)OH)CH₂(C(═O)OCH₃)E-33 CH₂CH₂CH₃ CH(C(═O)OH)CH₂(C(═O)OCH₃) E-34 CH(CH₃)₂CH(C(═O)OH)CH₂(C(═O)OCH₃) E-35 benzyl CH(C(═O)OH)CH₂(C(═O)OCH₃) E-36allyl CH(C(═O)OH)CH₂(C(═O)OCH₃) E-37 CH₃ CH(C(═O)OH)CH₂(C(═O)OCH₂CH₃)E-38 CH₂CH₃ CH(C(═O)OH)CH₂(C(═O)OCH₂CH₃) E-39 CH₂CH₂CH₃CH(C(═O)OH)CH₂(C(═O)OCH₂CH₃) E-40 CH(CH₃)₂ CH(C(═O)OH)CH₂(C(═O)OCH₂CH₃)E-41 benzyl CH(C(═O)OH)CH₂(C(═O)OCH₂CH₃) E-42 allylCH(C(═O)OH)CH₂(C(═O)OCH₂CH₃) E-43 CH₃ CH(C(═O)OH)CH₂(C(═O)OCH₂CH₂CH₃)E-44 CH₂CH₃ CH(C(═O)OH)CH₂(C(═O)OCH₂CH₂CH₃) E-45 CH₂CH₂CH₃CH(C(═O)OH)CH₂(C(═O)OCH₂CH₂CH₃) E-46 CH(CH₃)₂CH(C(═O)OH)CH₂(C(═O)OCH₂CH₂CH₃) E-47 benzylCH(C(═O)OH)CH₂(C(═O)OCH₂CH₂CH₃) E-48 allylCH(C(═O)OH)CH₂(C(═O)OCH₂CH₂CH₃) E-49 CH₃ CH(C(═O)OH)CH₂(C(═O)OCH(CH₃)₂)E-50 CH₂CH₃ CH(C(═O)OH)CH₂(C(═O)OCH(CH₃)₂) E-51 CH₂CH₂CH₃CH(C(═O)OH)CH₂(C(═O)OCH(CH₃)₂) E-52 CH(CH₃)₂CH(C(═O)OH)CH₂(C(═O)OCH(CH₃)₂) E-53 benzylCH(C(═O)OH)CH₂(C(═O)OCH(CH₃)₂) E-54 allyl CH(C(═O)OH)CH₂(C(═O)OCH(CH₃)₂)E-55 CH₃ CH(C(═O)OCH₃)CH₂(C(═O)OCH₃) E-56 CH₂CH₃CH(C(═O)OCH₃)CH₂(C(═O)OCH₃) E-57 CH₂CH₂CH₃ CH(C(═O)OCH₃)CH₂(C(═O)OCH₃)E-58 CH(CH₃)₂ CH(C(═O)OCH₃)CH₂(C(═O)OCH₃) E-59 benzylCH(C(═O)OCH₃)CH₂(C(═O)OCH₃) E-60 allyl CH(C(═O)OCH₃)CH₂(C(═O)OCH₃) E-61CH₃ CH(C(═O)OCH₃)CH₂(C(═O)OCH₂CH₃) E-62 CH₂CH₃CH(C(═O)OCH₃)CH₂(C(═O)OCH₂CH₃) E-63 CH₂CH₂CH₃CH(C(═O)OCH₃)CH₂(C(═O)OCH₂CH₃) E-64 CH(CH₃)₂CH(C(═O)OCH₃)CH₂(C(═O)OCH₂CH₃) E-65 benzylCH(C(═O)OCH₃)CH₂(C(═O)OCH₂CH₃) E-66 allyl CH(C(═O)OCH₃)CH₂(C(═O)OCH₂CH₃)E-67 CH₃ CH(C(═O)OCH₃)CH₂(C(═O)OCH₂CH₂CH₃) E-68 CH₂CH₃CH(C(═O)OCH₃)CH₂(C(═O)OCH₂CH₂CH₃) E-69 CH₂CH₂CH₃CH(C(═O)OCH₃)CH₂(C(═O)OCH₂CH₂CH₃) E-70 CH(CH₃)₂CH(C(═O)OCH₃)CH₂(C(═O)OCH₂CH₂CH₃) E-71 benzylCH(C(═O)OCH₃)CH₂(C(═O)OCH₂CH₂CH₃) E-72 allylCH(C(═O)OCH₃)CH₂(C(═O)OCH₂CH₂CH₃) E-73 CH₃CH(C(═O)OCH₃)CH₂(C(═O)OCH(CH₃)₂) E-74 CH₂CH₃CH(C(═O)OCH₃)CH₂(C(═O)OCH(CH₃)₂) E-75 CH₂CH₂CH₃CH(C(═O)OCH₃)CH₂(C(═O)OCH(CH₃)₂) E-76 CH(CH₃)₂CH(C(═O)OCH₃)CH₂(C(═O)OCH(CH₃)₂) E-77 benzylCH(C(═O)OCH₃)CH₂(C(═O)OCH(CH₃)₂) E-78 allylCH(C(═O)OCH₃)CH₂(C(═O)OCH(CH₃)₂) E-79 CH₃ CH(C(═O)OCH₂CH₃)CH₂(C(═O)OCH₃)E-80 CH₂CH₃ CH(C(═O)OCH₂CH₃)CH₂(C(═O)OCH₃) E-81 CH₂CH₂CH₃CH(C(═O)OCH₂CH₃)CH₂(C(═O)OCH₃) E-82 CH(CH₃)₂CH(C(═O)OCH₂CH₃)CH₂(C(═O)OCH₃) E-83 benzylCH(C(═O)OCH₂CH₃)CH₂(C(═O)OCH₃) E-84 allyl CH(C(═O)OCH₂CH₃)CH₂(C(═O)OCH₃)E-85 CH₃ CH(C(═O)OCH₂CH₃)CH₂(C(═O)OCH₂CH₃) E-86 CH₂CH₃CH(C(═O)OCH₂CH₃)CH₂(C(═O)OCH₂CH₃) E-87 CH₂CH₂CH₃CH(C(═O)OCH₂CH₃)CH₂(C(═O)OCH₂CH₃) E-88 CH(CH₃)₂CH(C(═O)OCH₂CH₃)CH₂(C(═O)OCH₂CH₃) E-89 benzylCH(C(═O)OCH₂CH₃)CH₂(C(═O)OCH₂CH₃) E-90 allylCH(C(═O)OCH₂CH₃)CH₂(C(═O)OCH₂CH₃) E-91 CH₃CH(C(═O)OCH₂CH₃)CH₂(C(═O)OCH₂CH₂CH₃) E-92 CH₂CH₃CH(C(═O)OCH₂CH₃)CH₂(C(═O)OCH₂CH₂CH₃) E-93 CH₂CH₂CH₃CH(C(═O)OCH₂CH₃)CH₂(C(═O)OCH₂CH₂CH₃) E-94 CH(CH₃)₂CH(C(═O)OCH₂CH₃)CH₂(C(═O)OCH₂CH₂CH₃) E-95 benzylCH(C(═O)OCH₂CH₃)CH₂(C(═O)OCH₂CH₂CH₃) E-96 allylCH(C(═O)OCH₂CH₃)CH₂(C(═O)OCH₂CH₂CH₃) E-97 CH₃CH(C(═O)OCH₂CH₃)CH₂(C(═O)OCH(CH₃)₂) E-98 CH₂CH₃CH(C(═O)OCH₂CH₃)CH₂(C(═O)OCH(CH₃)₂) E-99 CH₂CH₂CH₃CH(C(═O)OCH₂CH₃)CH₂(C(═O)OCH(CH₃)₂) E-100 CH(CH₃)₂CH(C(═O)OCH₂CH₃)CH₂(C(═O)OCH(CH₃)₂) E-101 benzylCH(C(═O)OCH₂CH₃)CH₂(C(═O)OCH(CH₃)₂) E-102 allylCH(C(═O)OCH₂CH₃)CH₂(C(═O)OCH(CH₃)₂) E-103 CH₃CH(C(═O)OCH₂CH₂CH₃)CH₂(C(═O)OCH₃) E-104 CH₂CH₃CH(C(═O)OCH₂CH₂CH₃)CH₂(C(═O)OCH₃) E-105 CH₂CH₂CH₃CH(C(═O)OCH₂CH₂CH₃)CH₂(C(═O)OCH₃) E-106 CH(CH₃)₂CH(C(═O)OCH₂CH₂CH₃)CH₂(C(═O)OCH₃) E-107 benzylCH(C(═O)OCH₂CH₂CH₃)CH₂(C(═O)OCH₃) E-108 allylCH(C(═O)OCH₂CH₂CH₃)CH₂(C(═O)OCH₃) E-109 CH₃CH(C(═O)OCH(CH₃)₂)CH₂(C(═O)OCH₃) E-110 CH₂CH₃CH(C(═O)OCH(CH₃)₂)CH₂(C(═O)OCH₃) E-111 CH₂CH₂CH₃CH(C(═O)OCH(CH₃)₂)CH₂(C(═O)OCH₃) E-112 CH(CH₃)₂CH(C(═O)OCH(CH₃)₂)CH₂(C(═O)OCH₃) E-113 benzylCH(C(═O)OCH(CH₃)₂)CH₂(C(═O)OCH₃) E-114 allylCH(C(═O)OCH(CH₃)₂)CH₂(C(═O)OCH₃) E-115 CH₃CH(C(═O)OCH₂CH₂CH₃)CH₂(C(═O)OCH₂CH₃) E-116 CH₂CH₃CH(C(═O)OCH₂CH₂CH₃)CH₂(C(═O)OCH₂CH₃) E-117 CH₂CH₂CH₃CH(C(═O)OCH₂CH₂CH₃)CH₂(C(═O)OCH₂CH₃) E-118 CH(CH₃)₂CH(C(═O)OCH₂CH₂CH₃)CH₂(C(═O)OCH₂CH₃) E-119 benzylCH(C(═O)OCH₂CH₂CH₃)CH₂(C(═O)OCH₂CH₃) E-120 allylCH(C(═O)OCH₂CH₂CH₃)CH₂(C(═O)OCH₂CH₃) E-121 CH₃CH(C(═O)OCH(CH₃)₂)CH₂(C(═O)OCH₂CH₃) E-122 CH₂CH₃CH(C(═O)OCH(CH₃)₂)CH₂(C(═O)OCH₂CH₃) E-123 CH₂CH₂CH₃CH(C(═O)OCH(CH₃)₂)CH₂(C(═O)OCH₂CH₃) E-124 CH(CH₃)₂CH(C(═O)OCH(CH₃)₂)CH₂(C(═O)OCH₂CH₃) E-125 benzylCH(C(═O)OCH(CH₃)₂)CH₂(C(═O)OCH₂CH₃) E-126 allylCH(C(═O)OCH(CH₃)₂)CH₂(C(═O)OCH₂CH₃) E-127 CH₃CH(C(═O)OCH₂CH₂CH₃)CH₂(C(═O)OCH₂CH₂CH₃) E-128 CH₂CH₃CH(C(═O)OCH₂CH₂CH₃)CH₂(C(═O)OCH₂CH₂CH₃) E-129 CH₂CH₂CH₃CH(C(═O)OCH₂CH₂CH₃)CH₂(C(═O)OCH₂CH₂CH₃) E-130 CH(CH₃)₂CH(C(═O)OCH₂CH₂CH₃)CH₂(C(═O)OCH₂CH₂CH₃) E-131 benzylCH(C(═O)OCH₂CH₂CH₃)CH₂(C(═O)OCH₂CH₂CH₃) E-132 allylCH(C(═O)OCH₂CH₂CH₃)CH₂(C(═O)OCH₂CH₂CH₃) E-133 CH₃CH(C(═O)OCH(CH₃)₂)CH₂(C(═O)OCH₂CH₂CH₃) E-134 CH₂CH₃CH(C(═O)OCH(CH₃)₂)CH₂(C(═O)OCH₂CH₂CH₃) E-135 CH₂CH₂CH₃CH(C(═O)OCH(CH₃)₂)CH₂(C(═O)OCH₂CH₂CH₃) E-136 CH(CH₃)₂CH(C(═O)OCH(CH₃)₂)CH₂(C(═O)OCH₂CH₂CH₃) E-137 benzylCH(C(═O)OCH(CH₃)₂)CH₂(C(═O)OCH₂CH₂CH₃) E-138 allylCH(C(═O)OCH(CH₃)₂)CH₂(C(═O)OCH₂CH₂CH₃) E-139 CH₃CH(C(═O)OCH₂CH₂CH₃)CH₂(C(═O)OCH(CH₃)₂) E-140 CH₂CH₃CH(C(═O)OCH₂CH₂CH₃)CH₂(C(═O)OCH(CH₃)₂) E-141 CH₂CH₂CH₃CH(C(═O)OCH₂CH₂CH₃)CH₂(C(═O)OCH(CH₃)₂) E-142 CH(CH₃)₂CH(C(═O)OCH₂CH₂CH₃)CH₂(C(═O)OCH(CH₃)₂) E-143 benzylCH(C(═O)OCH₂CH₂CH₃)CH₂(C(═O)OCH(CH₃)₂) E-144 allylCH(C(═O)OCH₂CH₂CH₃)CH₂(C(═O)OCH(CH₃)₂) E-145 CH₃CH(C(═O)OCH(CH₃)₂)CH₂(C(═O)OCH(CH₃)₂) E-146 CH₂CH₃CH(C(═O)OCH(CH₃)₂)CH₂(C(═O)OCH(CH₃)₂) E-147 CH₂CH₂CH₃CH(C(═O)OCH(CH₃)₂)CH₂(C(═O)OCH(CH₃)₂) E-148 CH(CH₃)₂CH(C(═O)OCH(CH₃)₂)CH₂(C(═O)OCH(CH₃)₂) E-149 benzylCH(C(═O)OCH(CH₃)₂)CH₂(C(═O)OCH(CH₃)₂) E-150 allylCH(C(═O)OCH(CH₃)₂)CH₂(C(═O)OCH(CH₃)₂)

Table 133

Compounds of the formula I.1(i), wherein R² is absent and thecombination of R^(N) (CHR^(a)NR^(e)(C═O)R^(f)) and R¹ corresponds ineach case to one row of Table F

Table 134

Compounds of the formula I.2(i), wherein R² is absent and thecombination of R^(N) (CHR^(a)NR^(e)(C═O)R^(f)) and R¹ corresponds ineach case to one row of Table F

Table 135

Compounds of the formula I.3(i), wherein R² is absent and thecombination of R^(N) (CHR^(a)NR^(e)(C═O)R^(f)) and R¹ corresponds ineach case to one row of Table F

Table 136

Compounds of the formula I.1(ii), wherein R² is CH₃ and the combinationof R^(N) (CHR^(a)NR^(e)(C═O)R^(f)) and R¹ corresponds in each case toone row of Table F

Table 137

Compounds of the formula I.1(iii), wherein R² is CH₃ and the combinationof R^(N) (CHR^(a)NR^(e)(C═O)R^(f)) and R¹ corresponds in each case toone row of Table F

Table 138

Compounds of the formula I.2(ii), wherein R² is CH₃ and the combinationof R^(N) (CHR^(a)NR^(e)(C═O)R^(f)) and R¹ corresponds in each case toone row of Table F

Table 139

Compounds of the formula I.2(iii), wherein R² is CH₃ and the combinationof R^(N) (CHR^(a)NR^(e)(C═O)R^(f)) and R¹ corresponds in each case toone row of Table F

Table 140

Compounds of the formula I.3(ii), wherein R² is CH₃ and the combinationof R^(N) (CHR^(a)NR^(e)(C═O)R^(f)) and R¹ corresponds in each case toone row of Table F

Table 141

Compounds of the formula I.3(iii), wherein R² is CH₃ and the combinationof R^(N)(CHR^(a)NR^(e)(C═O)R^(f)) and R¹ corresponds in each case to onerow of Table F

Table 142

Compounds of the formula I.1(ii), wherein R² is CH₂CH₃ and thecombination of R^(N)(CHR^(a)NR^(e)(C═O)R^(f)) and R¹ corresponds in eachcase to one row of Table F

Table 143

Compounds of the formula I.1(iii), wherein R² is CH₂CH₃ and thecombination of R^(N)(CHR^(a)NR^(e)(C═O)R^(f)) and R¹ corresponds in eachcase to one row of Table F

Table 144

Compounds of the formula I.2(ii), wherein R² is CH₂CH₃ and thecombination of R^(N)(CHR^(a)NR^(e)(C═O)R^(f)) and R¹ corresponds in eachcase to one row of Table F

Table 145

Compounds of the formula I.2(iii), wherein R² is CH₂CH₃ and thecombination of R^(N)(CHR^(a)NR^(e)(C═O)R^(f)) and R¹ corresponds in eachcase to one row of Table F

Table 146

Compounds of the formula I.3(ii), wherein R² is CH₂CH₃ and thecombination of R^(N)(CHR^(a)NR^(e)(C═O)R^(f)) and R¹ corresponds in eachcase to one row of Table F

Table 147

Compounds of the formula I.3(iii), wherein R² is CH₂CH₃ and thecombination of R^(N)(CHR^(a)NR^(e)(C═O)R^(f)) and R¹ corresponds in eachcase to one row of Table F

Table 148

Compounds of the formula I.1(ii), wherein R² is CH₂CH₂CH₃ and thecombination of R^(N)(CHR^(a)NR^(e)(C═O)R^(f)) and R¹ corresponds in eachcase to one row of Table F

Table 149

Compounds of the formula I.1(ii), wherein R² is CH(CH₃)₂ and thecombination of R^(N)(CHR^(a)NR^(e)(C═O)R^(f)) and R¹ corresponds in eachcase to one row of Table F

Table 150

Compounds of the formula I.1(iii), wherein R² is CH₂CH₂CH₃ and thecombination of R^(N)(CHR^(a)NR^(e)(C═O)R^(f)) and R¹ corresponds in eachcase to one row of Table F

Table 151

Compounds of the formula I.1(iii), wherein R² is CH(CH₃)₂ and thecombination of R^(N)(CHR^(a)NR^(e)(C═O)R^(f)) and R¹ corresponds in eachcase to one row of Table F

Table 152

Compounds of the formula I.2(ii), wherein R² is CH₂CH₂CH₃ and thecombination of R^(N)(CHR^(a)NR^(e)(C═O)R^(f)) and R¹ corresponds in eachcase to one row of Table F

Table 153

Compounds of the formula I.2(ii), wherein R² is CH(CH₃)₂ and thecombination of R^(N)(CHR^(a)NR^(e)(C═O)R^(f)) and R¹ corresponds in eachcase to one row of Table F

Table 154

Compounds of the formula I.2(iii), wherein R² is CH₂CH₂CH₃ and thecombination of R^(N)(CHR^(a)NR^(e)(C═O)R^(f)) and R¹ corresponds in eachcase to one row of Table F

Table 155

Compounds of the formula I.2(iii), wherein R² is CH(CH₃)₂ and thecombination of R^(N)(CHR^(a)NR^(e)(C═O)R^(f)) and R¹ corresponds in eachcase to one row of Table F

Table 156

Compounds of the formula I.3(ii), wherein R² is CH₂CH₂CH₃ and thecombination of R^(N)(CHR^(a)NR^(e)(C═O)R¹) and R¹ corresponds in eachcase to one row of Table F

Table 157

Compounds of the formula I.3(ii), wherein R² is CH(CH₃)₂ and thecombination of R^(N)(CHR^(a)NR^(e)(C═O)R^(f)) and R¹ corresponds in eachcase to one row of Table F

Table 158

Compounds of the formula I.3(iii), wherein R² is CH₂CH₂CH₃ and thecombination of R^(N)(CHR^(a)NR^(e)(C═O)R¹) and R¹ corresponds in eachcase to one row of Table F

Table 159

Compounds of the formula I.3(iii), wherein R² is CH(CH₃)₂ and thecombination of R^(N)(CHR^(a)NR^(e)(C═O)R^(f)) and R¹ corresponds in eachcase to one row of Table F

Table 160

Compounds of the formula I.1(ii), wherein R² is phenyl and thecombination of R^(N)(CHR^(a)NR^(e)(C═O)R¹) and R¹ corresponds in eachcase to one row of Table F

Table 161

Compounds of the formula I.1(iii), wherein R² is phenyl and thecombination of R^(N)(CHR^(a)NR^(e)(C═O)R^(f)) and R¹ corresponds in eachcase to one row of Table F

Table 162

Compounds of the formula I.2(ii), wherein R² is phenyl and thecombination of R^(N)(CHR^(a)NR^(e)(C═O)R¹) and R¹ corresponds in eachcase to one row of Table F

Table 163

Compounds of the formula I.2(iii), wherein R² is phenyl and thecombination of R^(N)(CHR^(a)NR^(e)(C═O)R^(f)) and R¹ corresponds in eachcase to one row of Table F

Table 164

Compounds of the formula I.3(ii), wherein R² is phenyl and thecombination of R^(N)(CHR^(a)NR^(e)(C═O)R¹) and R¹ corresponds in eachcase to one row of Table F

Table 165

Compounds of the formula I.3(iii), wherein R² is phenyl and thecombination of R^(N) (CHR^(a)NR^(e)(C═O)R^(f)) and R¹ corresponds ineach case to one row of Table F

TABLE F No. R¹ R^(N) (CHR^(a)NR^(e)(C═O)R^(f)) F-1 CH₃ CH₂NH(C═O)H F-2CH₂CH₃ CH₂NH(C═O)H F-3 CH₂CH₂CH₃ CH₂NH(C═O)H F-4 CH(CH₃)₂ CH₂NH(C═O)HF-5 benzyl CH₂NH(C═O)H F-6 allyl CH₂NH(C═O)H F-7 CH₃ CH₂NH(C═O)CH₃ F-8CH₂CH₃ CH₂NH(C═O)CH₃ F-9 CH₂CH₂CH₃ CH₂NH(C═O)CH₃ F-10 CH(CH₃)₂CH₂NH(C═O)CH₃ F-11 benzyl CH₂NH(C═O)CH₃ F-12 allyl CH₂NH(C═O)CH₃

It has been found that the compounds as defined in the above tables arenot only advantageous in terms of reducing nitrification, but also inview of the fact that they have advantageous properties, e.g., in termsof their low volatility and/or their environmental safety. Furthermore,the compounds according to the present invention can cost-efficiently beprepared.

It is to be understood that also combinations of the above compounds maybe used as nitrification inhibitors according to the present invention,in particular combinations of compounds, which are obtained as isomermixtures after the N-substituent has been introduced as outlined above.

In connection with the methods, uses, compositions, and mixtures of theinvention, and in particular with a view to their use, the followingpreferred embodiments are additionally relevant:

In a central aspect the present invention thus relates to the use of acompound of formula I as defined herein as a nitrification inhibitor, orto the use of a composition comprising said compound of formula I asdefined herein for reducing nitrification. The compound of formula I orderivatives or salts thereof as defined herein, in particular thecompounds of formula I and/or salts or suitable derivatives thereof, aswell as compositions comprising said compound of formula I, oragrochemical mixtures comprising said compound of formula I may be usedfor reducing nitrification.

The use may be based on the application of the nitrification inhibitor,the composition or the agrochemical mixture as defined herein to a plantgrowing on soil and/or the locus where the plant is growing or isintended to grow, or the use may be based on the application of thenitrification inhibitor, the composition or the agrochemical mixture asdefined herein to soil where a plant is growing or is intended to growor to soil substituents. In specific embodiments, the nitrificationinhibitor may be used for reducing nitrification in the absence ofplants, e.g. as preparatory activity for subsequent agriculturalactivity, or for reducing nitrification in other technical areas, whichare not related to agriculture, e.g. for environmental, waterprotection, energy production or similar purposes. In specificembodiments, the nitrification inhibitor, or a composition comprisingsaid nitrification inhibitor according to the present invention may beused for the reduction of nitrification in sewage, slurry, manure ordung of animals, e.g. swine or bovine feces. For example, thenitrification inhibitor, or a composition comprising said nitrificationinhibitor according to the present invention may be used for thereduction of nitrification in sewage plants, biogas plants, cowsheds,liquid manure tanks or containers etc. Furthermore, the nitrificationinhibitor, or a composition comprising said nitrification inhibitor maybe used in exhaust air systems, preferably in exhaust air systems ofstables or cowsheds. The present invention therefore also relates to theuse of compounds of formula I for treating exhaust air, preferably theexhaust air of stables and cowsheds. In further embodiments, thenitrification inhibitor, or a composition comprising said nitrificationinhibitor according to the present invention may be used for thereduction of nitrification in situ in animals, e.g. in productivelivestock. Accordingly, the nitrification inhibitor, or a compositioncomprising said nitrification inhibitor according to the presentinvention may be fed to an animal, e.g. a mammal, for instance togetherwith suitable feed and thereby lead to a reduction of nitrification inthe gastrointestinal tract of the animals, which in turn is resulting inreduction of emissions from the gastrointestinal tract. This activity,i.e. the feeding of nitrification inhibitor, or a composition comprisingsaid nitrification inhibitor according to the present invention may berepeated one to several times, e.g. each 2^(nd), 3^(rd), 4^(th), 5^(th),6^(th), 7^(th) day, or each week, 2 weeks, 3 weeks, or month, 2 monthsetc.

The use may further include the application of a nitrification inhibitoror derivatives or salts thereof as defined herein above, in particularcompounds of formula I and/or salts or suitable derivatives thereof, aswell as compositions comprising said nitrification inhibitor, oragrochemical mixtures comprising said nitrification inhibitor as definedherein above to environments, areas or zones, where nitrification takesplace or is assumed or expected to take place. Such environments, areasor zones may not comprise plants or soil. For example, the inhibitorsmay be used for nitrification inhibition in laboratory environments,e.g. based on enzymatic reactions or the like. Also envisaged is the usein green houses or similar indoor facilities.

The term “reducing nitrification” or “reduction of nitrification” asused herein refers to a slowing down or stopping of nitrificationprocesses, e.g. by retarding or eliminating the natural transformationof ammonium into nitrate. Such reduction may be a complete or partialelimination of nitrification at the plant or locus where the inhibitoror composition comprising said inhibitor is applied. For example, apartial elimination may result in a residual nitrification on or in theplant, or in or on the soil or soil substituents where a plant grows oris intended to grow of about 90% to 1%, e.g. 90%, 85%, 80%, 70%, 60%,50%, 40%, 30%, 20%, 10% or less than 10%, e.g. 5% or less than 5% incomparison to a control situation where the nitrification inhibitor isnot used. In certain embodiments, a partial elimination may result in aresidual nitrification on or in the plant or in or on the soil or soilsubstituents where a plant grows or is intended to grow of below 1%,e.g. at 0.5%, 0.1% or less in comparison to a control situation wherethe nitrification inhibitor is not used.

The use of a nitrification inhibitor as defined herein above, or of acomposition as defined herein for reducing nitrification may be a singleuse, or it may be a repeated use. As single use, the nitrificationinhibitor or corresponding compositions may be provided to their targetsites, e.g. soil or loci, or objects, e.g. plants, only once in aphysiologically relevant time interval, e.g. once a year, or once every2 to 5 years, or once during the lifetime of a plant.

In other embodiments, the use may be repeated at least once per timeperiod, e.g. the nitrification inhibitor as defined herein above, or acomposition as defined herein may be used for reducing nitrification attheir target sites or objects two times within a time interval of days,weeks or months. The term “at least once” as used in the context of ause of the nitrification inhibitor means that the inhibitor may be usedtwo times, or several times, i.e. that a repetition or multiplerepetitions of an application or treatment with a nitrificationinhibitor may be envisaged. Such a repetition may be a 2 times, 3 times,4 times, 5 times, 6 times, 7 times, 8 times, 9 times, 10 times or morefrequent repetition of the use.

The nitrification inhibitor according to the present invention may beused in any suitable form. For example, it may be used as coated oruncoated granule, in liquid or semi-liquid form, as sprayable entity, orin irrigation approaches etc. In specific embodiments, the nitrificationinhibitor as defined herein may be applied or used as such, i.e. withoutformulations, fertilizer, additional water, coatings, or any furtheringredient.

The term “irrigation” as used herein refers to the watering of plants orloci or soils or soil substituents where a plant grows or is intended togrow, wherein said watering includes the provision of the nitrificationinhibitor according to the present invention together with water.

In a further aspect the invention relates to a composition for reducingnitrification comprising at least one nitrification inhibitor whereinsaid nitrification inhibitor is a compound of formula I or a derivativeas defined herein above; and at least one carrier.

The term “composition for reducing nitrification” as used herein refersto a composition which is suitable, e.g. comprises effectiveconcentrations and amounts of ingredients such as nitrificationinhibitors, in particular compounds of formula I or derivatives asdefined herein, for reducing nitrification in any context or environmentin which nitrification may occur. In one embodiment, the nitrificationmay be reduced in or on or at the locus of a plant. Typically, thenitrification may be reduced in the root zone of a plant. However, thearea in which such reduction of nitrification may occur is not limitedto the plants and their environment, but may also include any otherhabitat of nitrifying bacteria or any site at which nitrifying enzymaticactivities can be found or can function in a general manner, e.g. sewageplants, biogas plants, animal effluents from productive livestock, e.g.cows, pigs etc. “Effective amounts” or “effective concentrations” ofnitrification inhibitors as defined herein may be determined accordingto suitable in vitro and in vivo testings known to the skilled person.These amounts and concentrations may be adjusted to the locus, plant,soil, climate conditions or any other suitable parameter which may havean influence on nitrification processes.

A “carrier” as used herein is a substance or composition whichfacilitates the delivery and/or release of the ingredients to the placeor locus of destination. The term includes, for instance, agrochemicalcarriers which facilitate the delivery and/or release of agrochemicalsin their field of use, in particular on or into plants.

Examples of suitable carriers include solid carriers such as phytogels,or hydrogels, or mineral earths e.g. silicates, silica gels, talc,kaolins, limestone, lime, chalk, bole, loess, clays, dolomite,diatomaceous earth, calcium sulfate, magnesium sulfate, magnesium oxide,ground synthetic materials, fertilizers, such as, e.g. an solid orliquid ammonium-containing inorganic fertilizer such as an NPKfertilizer, ammonium nitrate, calcium ammonium nitrate, ammonium sulfatenitrate, ammonium sulfate or ammonium phosphate; an solid or liquidorganic fertilizer such as liquid manure, semi-liquid manure, stablemanure, biogas manure and straw manure, worm castings, compost, seaweedor guano, or an urea-containing fertilizer such as urea, formaldehydeurea, anhydrous ammonium, urea ammonium nitrate (UAN) solution, ureasulphur, stabilized urea, urea based NPK-fertilizers, or urea ammoniumsulfate, and products of vegetable origin, such as cereal meal, treebark meal, wood meal and nutshell meal, cellulose powders and othersolid carriers. Further suitable examples of carriers include fumedsilica or precipitated silica, which may, for instance, be used in solidformulations as flow aid, anti-caking aid, milling aid and as carrierfor liquid active ingredients. Additional examples of suitable carriersare microparticles, for instance microparticles which stick to plantleaves and release their content over a certain period of time. Inspecific embodiments, agrochemical carriers such as composite gelmicroparticles that can be used to deliver plant-protection activeprinciples, e.g. as described in U.S. Pat. No. 6,180,141; orcompositions comprising at least one phytoactive compound and anencapsulating adjuvant, wherein the adjuvant comprises a fungal cell ora fragment thereof, e.g. as described in WO 2005/102045; or carriergranules, coated with a lipophilic tackifier on the surface, wherein thecarrier granule adheres to the surface of plants, grasses and weeds,e.g. as disclosed in US 2007/0280981 may be used. In further specificembodiments, such carriers may include specific, strongly bindingmolecule which assure that the carrier sticks to the plant, the seed,and/or loci where the plant is growing or is intended to grow, till itscontent is completely delivered. For instance, the carrier may be orcomprise cellulose binding domains (CBDs) have been described as usefulagents for attachment of molecular species to cellulose (see U.S. Pat.No. 6,124,117); or direct fusions between a CBD and an enzyme; or amultifunctional fusion protein which may be used for delivery ofencapsulated agents, wherein the multifunctional fusion proteins mayconsist of a first binding domain which is a carbohydrate binding domainand a second binding domain, wherein either the first binding domain orthe second binding domain can bind to a microparticle (see also WO03/031477). Further suitable examples of carriers include bifunctionalfusion proteins consisting of a CBD and an anti-RR6 antibody fragmentbinding to a microparticle, which complex may be deposited onto treadsor cut grass (see also WO 03/031477). In another specific embodiment thecarrier may be active ingredient carrier granules that adhere to e.g.the surface of plants, grasses, weeds, seeds, and/or loci where theplant is growing or is intended to grow etc. using a moisture-activecoating, for instance including gum arabic, guar gum, gum karaya, gumtragacanth and locust bean gum. Upon application of the inventivegranule onto a plant surface, water from precipitation, irrigation, dew,co-application with the granules from special application equipment, orguttation water from the plant itself may provide sufficient moisturefor adherence of the granule to the plant surface (see also US2007/0280981).

In another specific embodiment the carrier, e.g. an agrochemicalcarrier, may be or comprise polyaminoacids. Polyaminoacids may beobtained according to any suitable process, e.g. by polymerization ofsingle or multiple amino acids such as glycine, alanine, valine,leucine, isoleucine, phenylalanine, proline, tryptophan, serine,tyrosine, cysteine, methionine, asparagine, glutamine, threonine,aspartic acid, glutamic acid, lysine, arginine, histidine and/orornithine. Polyaminoacids may be combined with a nitrification inhibitoraccording to the present invention and, in certain embodiments, alsowith further carriers as mentioned herein above, or other nitrificationinhibitors as mentioned herein in any suitable ratio. For example,Polyaminoacids may be combined with a nitrification inhibitor accordingto the present invention in a ratio of 1 to 10 (polyaminoacids) vs. 0.5to 2 (nitrification inhibitor according to the present invention).

The composition for reducing nitrification comprising at least onenitrification inhibitor as defined herein may further compriseadditional ingredients, for example at least one pesticidal compound.For example, the composition may additionally comprise at least oneherbicidal compound and/or at least one fungicidal compound and/or atleast one insecticidal compound and/or at least one nematicide and/or atleast one biopesticide and/or at least one biostimulant.

In further embodiments, the composition may, in addition to the aboveindicated ingredients, in particular in addition to the nitrificationinhibitor of the compound of formula I, further comprise one or morealternative or additional nitrification inhibitors. Examples ofenvisaged alternative or additional nitrification inhibitors arelinoleic acid, alpha-linolenic acid, methyl p-coumarate, methylferulate, methyl 3-(4-hydroxyphenyl) propionate (MHPP), Karanjin,brachialacton, p-benzoquinone sorgoleone,2-chloro-6-(trichloromethyl)-pyridine (nitrapyrin or N-serve),dicyandiamide (DCD, DIDIN), 3,4-dimethyl pyrazole phosphate (DMPP,ENTEC), 4-amino-1,2,4-triazole hydrochloride (ATC), 1-amido-2-thiourea(ASU), 2-amino-4-chloro-6-methylpyrimidine (AM),2-mercapto-benzothiazole (MBT),5-ethoxy-3-trichloromethyl-1,2,4-thiodiazole (terrazole, etridiazole),2-sulfanilamidothiazole (ST), ammoniumthiosulfate (ATU), 3-methylpyrazol(3-MP), 3,5-dimethylpyrazole (DMP), 1,2,4-triazol thiourea (TU),N-(1H-pyrazolyl-methyl)acetamides such asN-((3(5)-methyl-1H-pyrazole-1-yl)methyl)acetamide, andN-(1H-pyrazolyl-methyl)formamides such asN-((3(5)-methyl-1H-pyrazole-1-yl)methyl formamide,N-(4-chloro-3(5)-methyl-pyrazole-1-ylmethyl)-formamide,N-(3(5),4-dimethyl-pyrazole-1-ylmethyl)-formamide, neem, products basedon ingredients of neem, cyan amide, melamine, zeolite powder, catechol,benzoquinone, sodium terta board, zinc sulfate.

In a preferred embodiment, the composition according to the presentinvention may comprise a combination of the nitrification inhibitor ofthe compound of formula I and 2-chloro-6-(trichloromethyl)-pyridine(nitrapyrin or N-serve).

In a further preferred embodiment, the composition according to thepresent invention may comprise a combination of the nitrificationinhibitor of the compound of formula I and5-ethoxy-3-trichloromethyl-1,2,4-thiodiazole (terrazole, etridiazole).

In a further preferred embodiment, the composition according to thepresent invention may comprise a combination of the nitrificationinhibitor of the compound of formula I and dicyandiamide (DCD, DIDIN).

In a further preferred embodiment, the composition according to thepresent invention may comprise a combination of the nitrificationinhibitor of the compound of formula I and 3,4-dimethyl pyrazolephosphate (DMPP, ENTEC).

In a further preferred embodiment, the composition according to thepresent invention may comprise a combination of the nitrificationinhibitor of the compound of formula I and2-amino-4-chloro-6-methylpyrimidine (AM).

In a further preferred embodiment, the composition according to thepresent invention may comprise a combination of the nitrificationinhibitor of the compound of formula I and 2-mercapto-benzothiazole(MBT).

In a further preferred embodiment, the composition according to thepresent invention may comprise a combination of the nitrificationinhibitor of the compound of formula I and 2-sulfanilamidothiazole (ST).

In a further preferred embodiment, the composition according to thepresent invention may comprise a combination of the nitrificationinhibitor of the compound of formula I and ammoniumthiosulfate (ATU).

In a further preferred embodiment, the composition according to thepresent invention may comprise a combination of the nitrificationinhibitor of the compound of formula I and 3-methylpyrazol (3-MP).

In a further preferred embodiment, the composition according to thepresent invention may comprise a combination of the nitrificationinhibitor of the compound of formula I and 3,5-dimethylpyrazole (DMP).

In a further preferred embodiment, the composition according to thepresent invention may comprise a combination of the nitrificationinhibitor of the compound of formula I and 1,2,4-triazol.

In a further preferred embodiment, the composition according to thepresent invention may comprise a combination of the nitrificationinhibitor of the compound of formula I and thiourea (TU).

In yet another preferred embodiment, the composition according to thepresent invention may comprise a combination of the nitrificationinhibitor of the compound of formula I and linoleic acid.

In yet another preferred embodiment, the composition according to thepresent invention may comprise a combination of the nitrificationinhibitor of the compound of formula I and alpha-linolenic acid.

In yet another preferred embodiment, the composition according to thepresent invention may comprise a combination of the nitrificationinhibitor of the compound of formula I and methyl p-coumarate.

In yet another preferred embodiment, the composition according to thepresent invention may comprise a combination of the nitrificationinhibitor of the compound of formula I and methyl 3-(4-hydroxyphenyl)propionate (MHPP).

In yet another preferred embodiment, the composition according to thepresent invention may comprise a combination of the nitrificationinhibitor of the compound of formula I and methyl ferulate.

In yet another preferred embodiment, the composition according to thepresent invention may comprise a combination of the nitrificationinhibitor of the compound of formula I and Karanjin.

In yet another preferred embodiment, the composition according to thepresent invention may comprise a combination of the nitrificationinhibitor of the compound of formula I and brachialacton.

In yet another preferred embodiment, the composition according to thepresent invention may comprise a combination of the nitrificationinhibitor of the compound of formula I and p-benzoquinone sorgoleone.

In yet another preferred embodiment, the composition according to thepresent invention may comprise a combination of the nitrificationinhibitor of the compound of formula I and 4-amino-1,2,4-triazolehydrochloride (ATC).

In yet another preferred embodiment, the composition according to thepresent invention may comprise a combination of the nitrificationinhibitor of the compound of formula I and 1-amido-2-thiourea (ASU).

In yet another preferred embodiment, the composition according to thepresent invention may comprise a combination of the nitrificationinhibitor of the compound of formula I andN-((3(5)-methyl-1H-pyrazole-1-yl)methyl)acetamide.

In yet another preferred embodiment, the composition according to thepresent invention may comprise a combination of the nitrificationinhibitor of the compound of formula I andN-((3(5)-methyl-1H-pyrazole-1-yl)methyl formamide.

In yet another preferred embodiment, the composition according to thepresent invention may comprise a combination of the nitrificationinhibitor of the compound of formula I andN-(4-chloro-3(5)-methyl-pyrazole-1-ylmethyl)-formamide.

In yet another preferred embodiment, the composition according to thepresent invention may comprise a combination of the nitrificationinhibitor of the compound of formula I andN-(3(5),4-dimethyl-pyrazole-1-ylmethyl)-formamide.

In yet another preferred embodiment, the composition according to thepresent invention may comprise a combination of the nitrificationinhibitor of the compound of formula I and neem or products based oningredients of neem.

In yet another preferred embodiment, the composition according to thepresent invention may comprise a combination of the nitrificationinhibitor of the compound of formula I and cyanamide.

In yet another preferred embodiment, the composition according to thepresent invention may comprise a combination of the nitrificationinhibitor of the compound of formula I and melamine.

In yet another preferred embodiment, the composition according to thepresent invention may comprise a combination of the nitrificationinhibitor of the compound of formula I and zeolite powder.

In yet another preferred embodiment, the composition according to thepresent invention may comprise a combination of the nitrificationinhibitor of the compound of formula I and batechol.

In yet another preferred embodiment, the composition according to thepresent invention may comprise a combination of the nitrificationinhibitor of the compound of formula I and benzoquinone.

In yet another preferred embodiment, the composition according to thepresent invention may comprise a combination of the nitrificationinhibitor of the compound of formula I and sodium terat borate.

In yet another preferred embodiment, the composition according to thepresent invention may comprise a combination of the nitrificationinhibitor of the compound of formula I and zinc sulfate.

In further embodiments, the composition according to the presentinvention may comprise a combination of the nitrification inhibitor ofthe compound of formula I and two entities selected from the groupcomprising: linoleic acid, alpha-linolenic acid, methyl p-coumarate,methyl ferulate, methyl 3-(4-hydroxyphenyl) propionate (MHPP), Karanjin,brachialacton, p-benzoquinone sorgoleone,2-chloro-6-(trichloromethyl)-pyridine (nitrapyrin or N-serve),dicyandiamide (DCD, DIDIN), 3,4-dimethyl pyrazole phosphate (DMPP,ENTEC), 4-amino-1,2,4-triazole hydrochloride (ATC), 1-amido-2-thiourea(ASU), 2-amino-4-chloro-6-methylpyrimidine (AM),2-mercapto-benzothiazole (MBT),5-ethoxy-3-trichloromethyl-1,2,4-thiodiazole (terrazole, etridiazole),2-sulfanilamidothiazole (ST), ammoniumthiosulfate (ATU), 3-methylpyrazol(3-MP), 3,5-dimethylpyrazole (DMP), 1,2,4-triazol and thiourea (TU),N-(1H-pyrazolyl-methyl)acetamides such asN-((3(5)-methyl-1H-pyrazole-1-yl)methyl)acetamide, andN-(1H-pyrazolyl-methyl)formamides such asN-((3(5)-methyl-1H-pyrazole-1-yl)methyl formamide,N-(4-chloro-3(5)-methyl-pyrazole-1-ylmethyl)-formamide, orN-(3(5),4-dimethyl-pyrazole-1-ylmethyl)-formamide neem, products basedon ingredients of neem, cyan amide, melamine, zeolite powder, catechol,benzoquinone, sodium terta board, zinc sulfate.

In yet another group of embodiments, the composition according to thepresent invention may comprise a combination of the nitrificationinhibitor of the compound of formula I and three, four or more entitiesselected from the group comprising: linoleic acid, alpha-linolenic acid,methyl p-coumarate, methyl ferulate, methyl 3-(4-hydroxyphenyl)propionate (MHPP), Karanjin, brachialacton, p-benzoquinone sorgoleone,2-chloro-6-(trichloromethyl)-pyridine (nitrapyrin or N-serve),dicyandiamide (DCD, DIDIN), 3,4-dimethyl pyrazole phosphate (DMPP,ENTEC), 4-amino-1,2,4-triazole hydrochloride (ATC), 1-amido-2-thiourea(ASU), 2-amino-4-chloro-6-methylpyrimidine (AM),2-mercapto-benzothiazole (MBT),5-ethoxy-3-trichloromethyl-1,2,4-thiodiazole (terrazole, etridiazole),2-sulfanilamidothiazole (ST) ammoniumthiosulfate (ATU), 3-methylpyrazol(3-MP), 3,5-dimethylpyrazole (DMP), 1,2,4-triazol and thiourea (TU),N-(1H-pyrazolyl-methyl)acetamides such asN-((3(5)-methyl-1H-pyrazole-1-yl)methyl)acetamide, andN-(1H-pyrazolyl-methyl)formamides such asN-((3(5)-methyl-1H-pyrazole-1-yl)methyl formamide,N-(4-chloro-3(5)-methyl-pyrazole-1-ylmethyl)-formamide, orN-(3(5),4-dimethyl-pyrazole-1-ylmethyl)-formamide neem, products basedon ingredients of neem, cyan amide, melamine, zeolite powder, catechol,benzoquinone, sodium terta board, zinc sulfate.

In further embodiments, the composition may, in addition to the aboveindicated ingredients, in particular in addition to the nitrificationinhibitor of the compound of formula I, further comprise one or moreurease inhibitors. Examples of envisaged urease inhibitors includeN-(n-butyl) thiophosphoric acid triamide (NBPT, Agrotain), N-(n-propyl)thiophosphoric acid triamide (NPPT), 2-nitrophenyl phosphoric triamide(2-NPT), further NXPTs known to the skilled person,phenylphosphorodiamidate (PPD/PPDA), hydroquinone, ammonium thiosulfate,and mixtures of NBPT and NPPT (see e.g. U.S. Pat. No. 8,075,659). Suchmixtures of NBPT and NPPT may comprise NBPT in amounts of from 40 to 95%wt.-% and preferably of 60 to 80% wt.-% based on the total amount ofactive substances. Such mixtures are marketed as LIMUS, which is acomposition comprising about 16.9 wt.-% NBPT and about 5.6 wt.-% NPPTand about 77.5 wt.-% of other ingredients including solvents andadjuvants.

In a preferred embodiment, the composition according to the presentinvention may comprise a combination of the nitrification inhibitor ofthe compound of formula I and N-(n-butyl) thiophosphoric acid triamide(NBPT, Agrotain).

In a further preferred embodiment, the composition according to thepresent invention may comprise a combination of the nitrificationinhibitor of the compound of formula I and phenylphosphorodiamidate(PPD/PPDA).

In a further preferred embodiment, the composition according to thepresent invention may comprise a combination of the nitrificationinhibitor of the compound of formula I and N-(n-propyl) thiophosphoricacid triamide (NPPT).

In a further preferred embodiment, the composition according to thepresent invention may comprise a combination of the nitrificationinhibitor of the compound of formula I and 2-nitrophenyl phosphorictriamide (2-NPT).

In a further preferred embodiment, the composition according to thepresent invention may comprise a combination of the nitrificationinhibitor of the compound of formula I and hydroquinone.

In a further preferred embodiment, the composition according to thepresent invention may comprise a combination of the nitrificationinhibitor of the compound of formula I and ammonium thiosulfate.

In yet another preferred embodiment, the composition according to thepresent invention may comprise a combination of the nitrificationinhibitor of the compound of formula I and neem.

In yet another preferred embodiment, the composition according to thepresent invention may comprise a combination of the nitrificationinhibitor of the compound of formula I and cyanamide.

In yet another preferred embodiment, the composition according to thepresent invention may comprise a combination of the nitrificationinhibitor of the compound of formula I and melamine.

In a further preferred embodiment, the composition according to thepresent invention may comprise a combination of the nitrificationinhibitor of the compound of formula I and a mixture of NBPT and NPPTsuch as LIMUS.

In further embodiments, the composition according to the presentinvention may comprise a combination of the nitrification inhibitor ofthe compound of formula I and two or more entities selected from thegroup comprising: N-(n-butyl) thiophosphoric acid triamide (NBPT,Agrotain), N-(n-propyl) thiophosphoric acid triamide (NPPT),2-nitrophenyl phosphoric triamide (2-NPT), further NXPTs known to theskilled person, phenylphosphorodiamidate (PPD/PPDA), hydroquinone,ammonium thiosulfate, and LIMUS.

In further embodiments, the composition may, in addition to one, more orall of the above indicated ingredients, in particular in addition to thenitrification inhibitor of the compound of formula I, further compriseone or more plant growth regulators. Examples of envisaged plant growthregulators are antiauxins, auxins, cytokinins, defoliants, ethylenemodulators, ethylene releasers, gibberellins, growth inhibitors,morphactins, growth retardants, growth stimulators, and furtherunclassified plant growth regulators.

Suitable examples of antiauxins to be used in a composition according tothe present invention are clofibric acid or 2,3,5-tri-iodobenzoic acid.

Suitable examples of auxins to be used in a composition according to thepresent invention are 4-CPA, 2,4-D, 2,4-DB, 2,4-DEP, dichlorprop,fenoprop, IAA (indole-3-acetic acid), IBA, naphthaleneacetamide,alpha-naphthaleneacetic acid, 1-naphthol, naphthoxyacetic acid,potassium naphthenate, sodium naphthenate or 2,4,5-T.

Suitable examples of cytokinins to be used in a composition according tothe present invention are 2iP, 6-Benzylaminopurine (6-BA) (═N-6Benzyladenine), 2,6-Dimethylpuridine (N-Oxide-2,6-Lultidine),2,6-Dimethylpyridine, kinetin, or zeatin.

Suitable examples of defoliants to be used in a composition according tothe present invention are calcium cyanamide, dimethipin, endothal,merphos, metoxuron, pentachlorophenol, thidiazuron, tribufos, ortributyl phosphorotrithioate.

Suitable examples of ethylene modulators to be used in a compositionaccording to the present invention are aviglycine, 1-methylcyclopropene(1-MCP) Prohexadione (prohexadione calcium), or trinexapac(Trinexapac-ethyl).

Suitable examples of ethylene releasers to be used in a compositionaccording to the present invention are ACC, etacelasil, ethephon, orglyoxime.

Suitable examples of gibberellins to be used in a composition accordingto the present invention are gibberelline or gibberellic acid.

Suitable examples of growth inhibitors to be used in a compositionaccording to the present invention are abscisic acid, S-abscisic acid,ancymidol, butralin, carbaryl, chlorphonium, chlorpropham, dikegulac,flumetralin, fluoridamid, fosamine, glyphosine, isopyrimol, jasmonicacid, maleic hydrazide, mepiquat (mepiquat chloride, mepiquatpentaborate), piproctanyl, prohydrojasmon, propham, or2,3,5-tri-iodobenzoic acid.

Suitable examples of morphactins to be used in a composition accordingto the present invention are chlorfluren, chlorflurenol,dichlorflurenol, or flurenol

Suitable examples of growth retardants to be used in a compositionaccording to the present invention are chlormequat (chlormequatchloride), daminozide, flurprimidol, mefluidide, paclobutrazol,tetcyclacis, uniconazole, metconazol.

Suitable examples of growth stimulators to be used in a compositionaccording to the present invention are brassinolide, forchlorfenuron, orhymexazol.

Suitable examples of further unclassified plant growth regulators to beused in a composition according to the present invention are amidochlor,benzofluor, buminafos, carvone, choline chloride, ciobutide, clofencet,cloxyfonac, cyanamide, cyclanilide, cycloheximide, cyprosulfamide,epocholeone, ethychlozate, ethylene, fenridazon, fluprimidol,fluthiacet, heptopargil, holosulf, inabenfide, karetazan, lead arsenate,methasulfocarb, pydanon, sintofen, diflufenzopyr or triapenthenol.

In a preferred embodiment, the composition according to the presentinvention may comprise a combination of the nitrification inhibitor ofthe compound of formula I and at least one compound selected from thegroup comprising: abscisic acid, amidochlor, ancymidol,6-benzylaminopurine (═N-6 benzyladenine), brassinolide, butralin,chlormequat (chlormequat chloride), choline chloride, cyclanilide,daminozide, diflufenzopyr, dikegulac, dimethipin, 2,6-dimethylpyridine,ethephon, flumetralin, flurprimidol, fluthiacet, forchlorfenuron,gibberellic acid, inabenfide, indole-3-acetic acid, maleic hydrazide,mefluidide, mepiquat (mepiquat chloride), 1-methylcyclopropene (1-MCP),naphthaleneacetic acid, N-6 benzyladenine, paclobutrazol, prohexadione(prohexadione calcium), prohydrojasmon, thidiazuron, triapenthenol,tributyl phosphorotrithioate, 2,3,5-tri-iodobenzoic acid,trinexapac-ethyl, and uniconazole.

In a preferred embodiment, the composition according to the presentinvention may comprise a combination of the nitrification inhibitor ofthe compound of formula I and clofibric acid.

In a further preferred embodiment, the composition according to thepresent invention may comprise a combination of the nitrificationinhibitor of the compound of formula I and 2,3,5-tri-iodobenzoic acid.

In a further preferred embodiment, the composition according to thepresent invention may comprise a combination of the nitrificationinhibitor of the compound of formula I and 4-CPA.

In a further preferred embodiment, the composition according to thepresent invention may comprise a combination of the nitrificationinhibitor of the compound of formula I and 2,4-D.

In a further preferred embodiment, the composition according to thepresent invention may comprise a combination of the nitrificationinhibitor of the compound of formula I and 2,4-DB.

In a further preferred embodiment, the composition according to thepresent invention may comprise a combination of the nitrificationinhibitor of the compound of formula I and 2,4-DEP.

In a further preferred embodiment, the composition according to thepresent invention may comprise a combination of the nitrificationinhibitor of the compound of formula I and dichlorprop.

In a further preferred embodiment, the composition according to thepresent invention may comprise a combination of the nitrificationinhibitor of the compound of formula I and fenoprop.

In a further preferred embodiment, the composition according to thepresent invention may comprise a combination of the nitrificationinhibitor of the compound of formula I and IAA (indole-3-acetic acid).

In a further preferred embodiment, the composition according to thepresent invention may comprise a combination of the nitrificationinhibitor of the compound of formula I and IBA.

In a further preferred embodiment, the composition according to thepresent invention may comprise a combination of the nitrificationinhibitor of the compound of formula I and naphthaleneacetamide.

In a further preferred embodiment, the composition according to thepresent invention may comprise a combination of the nitrificationinhibitor of the compound of formula I and alpha-naphthaleneacetic acid.

In a further preferred embodiment, the composition according to thepresent invention may comprise a combination of the nitrificationinhibitor of the compound of formula I and 1-naphthol.

In a further preferred embodiment, the composition according to thepresent invention may comprise a combination of the nitrificationinhibitor of the compound of formula I and naphthoxyacetic acid.

In a further preferred embodiment, the composition according to thepresent invention may comprise a combination of the nitrificationinhibitor of the compound of formula I and potassium naphthenate.

In a further preferred embodiment, the composition according to thepresent invention may comprise a combination of the nitrificationinhibitor of the compound of formula I and sodium naphthenate.

In a further preferred embodiment, the composition according to thepresent invention may comprise a combination of the nitrificationinhibitor of the compound of formula I and 2,4,5-T.

In a further preferred embodiment, the composition according to thepresent invention may comprise a combination of the nitrificationinhibitor of the compound of formula I and 2iP.

In a further preferred embodiment, the composition according to thepresent invention may comprise a combination of the nitrificationinhibitor of the compound of formula I and 6-Benzylaminopurine (6-BA)(═N-6 Benzyladenine).

In a further preferred embodiment, the composition according to thepresent invention may comprise a combination of the nitrificationinhibitor of the compound of formula I and 2,6-Dimethylpuridine(N-Oxide-2,6-Lultidine).

In a further preferred embodiment, the composition according to thepresent invention may comprise a combination of the nitrificationinhibitor of the compound of formula I and zeatin.

In a further preferred embodiment, the composition according to thepresent invention may comprise a combination of the nitrificationinhibitor of the compound of formula I and kinetin.

In a further preferred embodiment, the composition according to thepresent invention may comprise a combination of the nitrificationinhibitor of the compound of formula I and calcium cyanamide.

In a further preferred embodiment, the composition according to thepresent invention may comprise a combination of the nitrificationinhibitor of the compound of formula I and dimethipin.

In a further preferred embodiment, the composition according to thepresent invention may comprise a combination of the nitrificationinhibitor of the compound of formula I and endothal.

In a further preferred embodiment, the composition according to thepresent invention may comprise a combination of the nitrificationinhibitor of the compound of formula I and merphos.

In a further preferred embodiment, the composition according to thepresent invention may comprise a combination of the nitrificationinhibitor of the compound of formula I and metoxuron.

In a further preferred embodiment, the composition according to thepresent invention may comprise a combination of the nitrificationinhibitor of the compound of formula I and pentachlorophenol.

In a further preferred embodiment, the composition according to thepresent invention may comprise a combination of the nitrificationinhibitor of the compound of formula I and thidiazuron.

In a further preferred embodiment, the composition according to thepresent invention may comprise a combination of the nitrificationinhibitor of the compound of formula I and tribufos.

In a further preferred embodiment, the composition according to thepresent invention may comprise a combination of the nitrificationinhibitor of the compound of formula I and tributyl phosphorotrithioate.

In a further preferred embodiment, the composition according to thepresent invention may comprise a combination of the nitrificationinhibitor of the compound of formula I and aviglycine.

In a further preferred embodiment, the composition according to thepresent invention may comprise a combination of the nitrificationinhibitor of the compound of formula I and 1-methylcyclopropene.

A composition as defined herein, in particular a composition comprisinga nitrification inhibitor as defined herein and a plant growth regulatoras defined herein, may be used for the increase of plant health.

The term “plant health” as used herein is intended to mean a conditionof the plant which is determined by several aspects alone or incombination with each other. One indicator (indicator 1) for thecondition of the plant is the crop yield. “Crop” and “fruit” are to beunderstood as any plant product which is further utilized afterharvesting, e.g. fruits in the proper sense, vegetables, nuts, grains,seeds, wood (e.g. in the case of silviculture plants), flowers (e.g. inthe case of gardening plants, ornamentals) etc., that is anything ofeconomic value that is produced by the plant. Another indicator(indicator 2) for the condition of the plant is the plant vigor. Theplant vigor becomes manifest in several aspects, too, some of which arevisual appearance, e.g. leaf color, fruit color and aspect, amount ofdead basal leaves and/or extent of leaf blades, plant weight, plantheight, extent of plant verse (lodging), number, strong ness andproductivity of tillers, panicles' length, extent of root system,strength of roots, extent of nodulation, in particular of rhizobialnodulation, point of time of germination, emergence, flowering, grainmaturity and/or senescence, protein content, sugar content and the like.Another indicator (indicator 3) for an increase of a plant's health isthe reduction of biotic or abiotic stress factors. The three abovementioned indicators for the health condition of a plant may beinterdependent and may result from each other. For example, a reductionof biotic or abiotic stress may lead to a better plant vigor, e.g. tobetter and bigger crops, and thus to an increased yield. Biotic stress,especially over longer terms, can have harmful effects on plants. Theterm “biotic stress” as used in the context of the present inventionrefers in particular to stress caused by living organisms.

As a result, the quantity and the quality of the stressed plants, theircrops and fruits decrease. As far as quality is concerned, reproductivedevelopment is usually severely affected with consequences on the cropswhich are important for fruits or seeds. Growth may be slowed by thestresses; polysaccharide synthesis, both structural and storage, may bereduced or modified: these effects may lead to a decrease in biomass andto changes in the nutritional value of the product. Abiotic stressincludes drought, cold, increased UV, increased heat, or other changesin the environment of the plant, that leads to sub-optimal growthconditions. The term “increased yield” of a plant as used herein meansthat the yield of a product of the respective plant is increased by ameasurable amount over the yield of the same product of the plantproduced under the same conditions, but without the application of thecomposition of the invention. According to the present invention, it ispreferred that the yield be increased by at least 0.5%, more preferredat least 1%, even more preferred at least 2%, still more preferred atleast 4%. An increased yield may, for example, be due to a reduction ofnitrification and a corresponding improvement of uptake of nitrogennutrients. The term “improved plant vigor” as used herein means thatcertain crop characteristics are increased or improved by a measurableor noticeable amount over the same factor of the plant produced underthe same conditions, but without the application of the composition ofthe present invention. Improved plant vigor can be characterized, amongothers, by following improved properties of a plant:

(a) improved vitality of the plant,

(b) improved quality of the plant and/or of the plant products, e.g.

(b) enhanced protein content,

(c) improved visual appearance,

(d) delay of senescence,

(e) enhanced root growth and/or more developed root system (e.g.determined by the dry mass of the root),

(f) enhanced nodulation, in particular rhizobial nodulation,

(g) longer panicles,

(h) bigger leaf blade,

(i) less dead basal leaves,

(j) increased chlorophyll content

(k) prolonged photosynthetically active period

(l) improved nitrogen-supply within the plant

The improvement of the plant vigor according to the present inventionparticularly means that the improvement of anyone or several or all ofthe above mentioned plant characteristics are improved. It further meansthat if not all of the above characteristics are improved, those whichare not improved are not worsened as compared to plants which were nottreated according to the invention or are at least not worsened to suchan extent that the negative effect exceeds the positive effect of theimproved characteristic (i.e. there is always an overall positive effectwhich preferably results in an improved crop yield). An improved plantvigor may, for example, be due to a reduction of nitrification and, e.g.a regulation of plant growth.

In further embodiments, the composition may, in addition to the aboveindicated ingredients, in particular in addition to the nitrificationinhibitor of the compound of formula I, further comprise one or morepesticides.

A pesticide is generally a chemical or biological agent (such aspesticidal active ingredient, compound, composition, virus, bacterium,antimicrobial or disinfectant) that through its effect deters,incapacitates, kills or otherwise discourages pests. Target pests caninclude insects, plant pathogens, weeds, mollusks, birds, mammals, fish,nematodes (roundworms), and microbes that destroy property, causenuisance, spread disease or are vectors for disease. The term“pesticide” includes also plant growth regulators that alter theexpected growth, flowering, or reproduction rate of plants; defoliantsthat cause leaves or other foliage to drop from a plant, usually tofacilitate harvest; desiccants that promote drying of living tissues,such as unwanted plant tops; plant activators that activate plantphysiology for defense of against certain pests; safeners that reduceunwanted herbicidal action of pesticides on crop plants; and plantgrowth promoters that affect plant physiology e.g. to increase plantgrowth, biomass, yield or any other quality parameter of the harvestablegoods of a crop plant.

Biopesticides have been defined as a form of pesticides based onmicro-organisms (bacteria, fungi, viruses, nematodes, etc.) or naturalproducts (compounds, such as metabolites, proteins, or extracts frombiological or other natural sources) (U.S. Environmental ProtectionAgency: http://www.epa.gov/pesticides/biopesticides/).

Biopesticides fall into two major classes, microbial and biochemicalpesticides:

-   -   (1) Microbial pesticides consist of bacteria, fungi or viruses        (and often include the metabolites that bacteria and fungi        produce). Entomopathogenic nematodes are also classed as        microbial pesticides, even though they are multi-cellular.    -   (2) Biochemical pesticides are naturally occurring substances        that control pests or provide other crop protection uses as        defined below, but are relatively non-toxic to mammals.

According to one embodiment, individual components of the compositionaccording to the invention such as parts of a kit or parts of a binaryor ternary mixture may be mixed by the user himself in a spray tank orany other kind of vessel used for applications (e.g. seed treater drums,seed pelleting machinery, knapsack sprayer) and further auxiliaries maybe added, if appropriate.

When living microorganisms, such as microbial pesticides from groupsL1), L3) and L5), form part of such kit, it must be taken care thatchoice and amounts of the components (e.g. chemical pesticides) and ofthe further auxiliaries should not influence the viability of themicrobial pesticides in the composition mixed by the user. Especiallyfor bactericides and solvents, compatibility with the respectivemicrobial pesticide has to be taken into account.

Consequently, one embodiment of the invention is a kit for preparing ausable pesticidal composition, the kit comprising a) a compositioncomprising component 1) as defined herein and at least one auxiliary;and b) a composition comprising component 2) as defined herein and atleast one auxiliary; and optionally c) a composition comprising at leastone auxiliary and optionally a further active component 3) as definedherein.

The following list of pesticides I (e.g. pesticidally-active substancesand biopesticides), in conjunction with which the compounds I can beused, is intended to illustrate the possible combinations but does notlimit them:

A) Respiration Inhibitors

-   -   Inhibitors of complex III at Q_(o) site: azoxystrobin (A.1.1),        coumethoxystrobin (A.1.2), coumoxystrobin (A.1.3), dimoxystrobin        (A.1.4), enestroburin (A.1.5), fenaminstrobin (A.1.6),        fenoxystrobin/flufenoxystrobin (A.1.7), fluoxastrobin (A.1.8),        kresoxim-methyl (A.1.9), mandestrobin (A.1.10), metominostrobin        (A.1.11), orysastrobin (A.1.12), picoxystrobin (A.1.13),        pyraclostrobin (A.1.14), pyrametostrobin (A.1.15),        pyraoxystrobin (A.1.16), trifloxy-strobin (A.1.17),        2-(2-(3-(2,6-dichlorophenyl)-1-methyl-allylideneaminooxymethyl)-phenyl)-2-methoxyimino-N-methyl-acetamide        (A.1.18), pyribencarb (A.1.19), triclopyricarb/chloro-dincarb        (A.1.20), famoxadone (A.1.21), fenamidone (A.1.21),        methyl-N-[2-[(1,4-dimethyl-5-phenyl-pyrazol-3-yl)oxylmethyl]phenyl]-N-methoxy-carbamate        (A.1.22),        1-[2-[[1-(4-chlorophenyl)pyrazol-3-yl]oxymethyl]-3-methyl-phenyl]-4-methyl-tetrazol-5-one        (A.1.25),        (Z,2E)-5-[1-(2,4-dichlorophenyl)pyrazol-3-yl]-oxy-2-methoxyimino-N,3-dimethyl-pent-3-enamide        (A.1.34),        (Z,2E)-5-[1-(4-chlorophenyl)pyrazol-3-yl]oxy-2-methoxyimino-N,3-dimethyl-pent-3-enamide        (A.1.35), pyriminostrobin (A.1.36), bifujunzhi (A.1.37),        2-(ortho-((2,5-dimethylphenyl-oxymethylen)phenyl)-3-methoxy-acrylic        acid methylester (A.1.38);    -   inhibitors of complex Ill at Q, site: cyazofamid (A.2.1),        amisulbrom (A.2.2),        [(6S,7R,8R)-8-benzyl-3-[(3-hydroxy-4-methoxy-pyridine-2-carbonyl)amino]-6-methyl-4,9-dioxo-1,5-dioxonan-7-yl]        2-methylpropanoate (A.2.3), fenpicoxamid (A.2.4);    -   inhibitors of complex II: benodanil (A.3.1), benzovindiflupyr        (A.3.2), bixafen (A.3.3), boscalid (A.3.4), carboxin (A.3.5),        fenfuram (A.3.6), fluopyram (A.3.7), flutolanil (A.3.8),        fluxapyroxad (A.3.9), furametpyr (A.3.10), isofetamid (A.3.11),        isopyrazam (A.3.12), mepronil (A.3.13), oxycarboxin (A.3.14),        penflufen (A.3.15), penthiopyrad (A.3.16), pydiflumetofen        (A.3.17), pyraziflumid (A.3.18), sedaxane (A.3.19), tecloftalam        (A.3.20), thifluzamide (A.3.21), inpyrfluxam (A.3.22),        pyrapropoyne (A.3.23), fluindapyr (A.3.28), methyl        (E)-2-[2-[(5-cyano-2-methyl-phenoxy)methyl]phenyl]-3-methoxy-prop-2-enoate        (A.3.30), isoflucypram (A.3.31),        2-(difluoromethyl)-N-(1,1,3-trimethyl-indan-4-yl)pyridine-3-carboxamide        (A.3.32),        2-(difluoromethyl)-N-[(3R)-1,1,3-trimethylindan-4-yl]pyridine-3-carboxamide        (A.3.33),        2-(difluoromethyl)-N-(3-ethyl-1,1-dimethyl-indan-4-yl)pyridine-3-carboxamide        (A.3.34),        2-(difluoromethyl)-N-[(3R)-3-ethyl-1,1-dimethyl-indan-4-yl]pyridine-3-carboxamide        (A.3.35),        2-(difluoromethyl)-N-(1,1-dimethyl-3-propyl-indan-4-yl)pyridine-3-carboxamide        (A.3.36),        2-(difluoromethyl)-N-[(3R)-1,1-dimethyl-3-propyl-indan-4-yl]pyridine-3-carboxamide        (A.3.37),        2-(difluoromethyl)-N-(3-isobutyl-1,1-dimethyl-indan-4-yl)        pyridine-3-carboxamide (A.3.38),        2-(difluoromethyl)-N-[(3R)-3-isobutyl-1,1-dimethyl-indan-4-yl]pyridine-3-carboxamide        (A.3.39);    -   other respiration inhibitors: diflumetorim (A.4.1); nitrophenyl        derivates: binapacryl (A.4.2), dinobuton (A.4.3), dinocap        (A.4.4), fluazinam (A.4.5), meptyldinocap (A.4.6), ferimzone        (A.4.7); organometal compounds: fentin salts, e.g.        fentin-acetate (A.4.8), fentin chloride (A.4.9) or fentin        hydroxide (A.4.10); ametoctradin (A.4.11); silthiofam (A.4.12);

B) Sterol Biosynthesis Inhibitors (SBI Fungicides)

-   -   C14 demethylase inhibitors: triazoles: azaconazole (B.1.1),        bitertanol (B.1.2), bromu-conazole (B.1.3), cyproconazole        (B.1.4), difenoconazole (B.1.5), diniconazole (B.1.6),        diniconazole-M (B.1.7), epoxiconazole (B.1.8), fenbuconazole        (B.1.9), fluquinconazole (B.1.10), flusilazole (B.1.11),        flutriafol (B.1.12), hexaconazole (B.1.13), imibenconazole        (B.1.14), ipconazole (B.1.15), metconazole (B.1.17),        myclobutanil (B.1.18), oxpoconazole (B.1.19), paclobutrazole        (B.1.20), penconazole (B.1.21), propiconazole (B.1.22),        prothio-conazole (B.1.23), simeconazole (B.1.24), tebuconazole        (B.1.25), tetraconazole (B.1.26), triadimefon (B.1.27),        triadimenol (B.1.28), triticonazole (B.1.29), uniconazole        (B.1.30),        2-(2,4-difluorophenyl)-1,1-difluoro-3-(tetrazol-1-yl)-1-[5-[4-(2,2,2-trifluoroethoxy)phenyl]-2-pyridyl]propan-2-ol        (B.1.31),        2-(2,4-difluorophenyl)-1,1-difluoro-3-(tetrazol-1-yl)-1-[5-[4-(trifluoromethoxy)phenyl]-2-pyridyl]propan-2-ol        (B.1.32), ipfentrifluconazole (B.1.37), mefentrifluconazole        (B.1.38),        2-(chloromethyl)-2-methyl-5-(p-tolylmethyl)-1-(1,2,4-triazol-1-ylmethyl)cyclopentanol        (B.1.43); imidazoles: imazalil (B.1.44), pefurazoate (B.1.45),        prochloraz (B.1.46), triflumizol (B.1.47); pyrimidines,        pyridines, piperazines: fe-narimol (B.1.49), pyrifenox (B.1.50),        triforine (B.1.51),        [3-(4-chloro-2-fluoro-phenyl)-5-(2,4-difluorophenyl)isoxazol-4-yl]-(3-pyridyl)methanol        (B.1.52);    -   Delta14-reductase inhibitors: aldimorph (B.2.1), dodemorph        (B.2.2), dodemorph-acetate (B.2.3), fenpropimorph (B.2.4),        tridemorph (B.2.5), fenpropidin (B.2.6), piperalin (B.2.7),        spiroxamine (B.2.8);    -   Inhibitors of 3-keto reductase: fenhexamid (B.3.1);    -   Other Sterol biosynthesis inhibitors: chlorphenomizole (B.4.1);

C) Nucleic Acid Synthesis Inhibitors

-   -   phenylamides or acyl amino acid fungicides: benalaxyl (C.1.1),        benalaxyl-M (C.1.2), kiralaxyl (C.1.3), metalaxyl (C.1.4),        metalaxyl-M (C.1.5), ofurace (C.1.6), oxadixyl (C.1.7);    -   other nucleic acid synthesis inhibitors: hymexazole (C.2.1),        octhilinone (C.2.2), oxolinic acid (C.2.3), bupirimate (C.2.4),        5-fluorocytosine (C.2.5),        5-fluoro-2-(p-tolylmethoxy)pyrimidin-4-amine (C.2.6),        5-fluoro-2-(4-fluorophenylmethoxy)pyrimidin-4-amine (C.2.7),        5-fluoro-2-(4-chlorophenylmethoxy)pyrimidin-4 amine (C.2.8);

D) Inhibitors of Cell Division and Cytoskeleton

-   -   tubulin inhibitors: benomyl (D.1.1), carbendazim (D.1.2),        fuberidazole (D1.3), thiabendazole (D.1.4), thiophanate-methyl        (D.1.5),        3-chloro-4-(2,6-difluorophenyl)-6-methyl-5-phenyl-pyridazine        (D.1.6),        3-chloro-6-methyl-5-phenyl-4-(2,4,6-trifluorophenyl)pyridazine        (D.1.7),        N-ethyl-2-[(3-ethynyl-8-methyl-6-quinolyl)oxy]butanamide        (D.1.8),        N-ethyl-2-[(3-ethynyl-8-methyl-6-quinolyl)oxy]-2-methylsulfanyl-acetamide        (D.1.9),        2-[(3-ethynyl-8-methyl-6-quinolyl)oxy]-N-(2-fluoroethyl)butanamide        (D.1.10),        2-[(3-ethynyl-8-methyl-6-quinolyl)oxy]-N-(2-fluoroethyl)-2-methoxy-acetamide        (D.1.11),        2-[(3-ethynyl-8-methyl-6-quinolyl)oxy]-N-propyl-butanamide        (D.1.12),        2-[(3-ethynyl-8-methyl-6-quinolyl)oxy]-2-methoxy-N-propyl-acetamide        (D.1.13),        2-[(3-ethynyl-8-methyl-6-quinolyl)oxy]-2-methylsulfanyl-N-propyl-acetamide        (D.1.14),        2-[(3-ethynyl-8-methyl-6-quinolyl)oxy]-N-(2-fluoroethyl)-2-methylsulfanyl-acetamide        (D.1.15),        4-(2-bromo-4-fluoro-phenyl)-N-(2-chloro-6-fluoro-phenyl)-2,5-dimethyl-pyrazol-3-amine        (D.1.16);    -   other cell division inhibitors: diethofencarb (D.2.1), ethaboxam        (D.2.2), pencycuron (D.2.3), fluopicolide (D.2.4), zoxamide        (D.2.5), metrafenone (D.2.6), pyriofenone (D.2.7);

E) Inhibitors of Amino Acid and Protein Synthesis

-   -   methionine synthesis inhibitors: cyprodinil (E.1.1), mepanipyrim        (E.1.2), pyrimethanil (E.1.3);    -   protein synthesis inhibitors: blasticidin-S(E.2.1), kasugamycin        (E.2.2), kasugamycin hydrochloride-hydrate (E.2.3), mildiomycin        (E.2.4), streptomycin (E.2.5), oxytetracyclin (E.2.6);

F) Signal Transduction Inhibitors

-   -   MAP/histidine kinase inhibitors: fluoroimid (F.1.1), iprodione        (F.1.2), procymidone (F.1.3), vinclozolin (F.1.4), fludioxonil        (F.1.5);    -   G protein inhibitors: quinoxyfen (F.2.1);

G) Lipid and Membrane Synthesis Inhibitors

-   -   Phospholipid biosynthesis inhibitors: edifenphos (G.1.1),        iprobenfos (G.1.2), pyrazophos (G.1.3), isoprothiolane (G.1.4);    -   lipid peroxidation: dicloran (G.2.1), quintozene (G.2.2),        tecnazene (G.2.3), tolclofos-methyl (G.2.4), biphenyl (G.2.5),        chloroneb (G.2.6), etridiazole (G.2.7);    -   phospholipid biosynthesis and cell wall deposition: dimethomorph        (G.3.1), flumorph (G.3.2), mandipropamid (G.3.3), pyrimorph        (G.3.4), benthiavalicarb (G.3.5), iprovalicarb (G.3.6),        valifenalate (G.3.7);    -   compounds affecting cell membrane permeability and fatty acids:        propamocarb (G.4.1);    -   inhibitors of oxysterol binding protein: oxathiapiprolin        (G.5.1),        2-{3-[2-(1-{[3,5-bis(di-fluoromethyl-1H-pyrazol-1-yl]acetyl}piperidin-4-yl)-1,3-thiazol-4-yl]-4,5-dihydro-1,2-oxazol-5-yl}phenyl        methanesulfonate (G.5.2),        2-{3-[2-(1-{[3,5-bis(difluoromethyl)-1H-pyrazol-1-yl]acetyl}piperidin-4-yl)        1,3-thiazol-4-yl]-4,5-dihydro-1,2-oxazol-5-yl}-3-chlorophenyl        methanesulfonate (G.5.3),        4-[1-[2-[3-(difluoromethyl)-5-methyl-pyrazol-1-yl]acetyl]-4-piperidyl]-N-tetralin-1-yl-pyridine-2-carboxamide        (G.5.4),        4-[1-[2-[3,5-bis(difluoromethyl)pyrazol-1-yl]acetyl]-4-piperidyl]-N-tetralin-1-yl-pyridine-2-carboxamide        (G.5.5),        4-[1-[2-[3-(difluoromethyl)-5-(trifluoromethyl)pyrazol-1-yl]acetyl]-4-piperidyl]-N-tetralin-1-yl-pyridine-2-carboxamide        (G.5.6),        4-[1-[2-[5-cyclopropyl-3-(difluoromethyl)pyrazol-1-yl]acetyl]-4-piperidyl]-N-tetralin-1-yl-pyridine-2-carboxamide        (G.5.7),        4-[1-[2-[5-methyl-3-(trifluoromethyl)pyrazol-1-yl]acetyl]-4-piperidyl]-N-tetralin-1-yl-pyridine-2-carboxamide        (G.5.8),        4-[1-[2-[5-(difluoromethyl)-3-(trifluoromethyl)pyrazol-1-yl]acetyl]-4-piperidyl]-N-tetralin-1-yl-pyridine-2-carboxamide        (G.5.9),        4-[1-[2-[3,5-bis(trifluoromethyl)pyrazol-1-yl]acetyl]-4-piperidyl]-N-tetralin-1-yl-pyridine-2-carboxamide        (G.5.10),        (4-[1-[2-[5-cyclopropyl-3-(trifluoromethyl)pyrazol-1-yl]acetyl]-4-piperidyl]-N-tetralin-1-yl-pyridine-2-carboxamide        (G.5.11);

H) Inhibitors with Multi Site Action

-   -   inorganic active substances: Bordeaux mixture (H.1.1), copper        (H.1.2), copper acetate (H.1.3), copper hydroxide (H.1.4),        copper oxychloride (H.1.5), basic copper sulfate (H.1.6), sulfur        (H.1.7);    -   thio- and dithiocarbamates: ferbam (H.2.1), mancozeb (H.2.2),        maneb (H.2.3), metam (H.2.4), metiram (H.2.5), propineb (H.2.6),        thiram (H.2.7), zineb (H.2.8), ziram (H.2.9);    -   organochlorine compounds: anilazine (H.3.1), chlorothalonil        (H.3.2), captafol (H.3.3), captan (H.3.4), folpet (H.3.5),        dichlofluanid (H.3.6), dichlorophen (H.3.7), hexachlorobenzene        (H.3.8), pentachlorphenole (H.3.9) and its salts, phthalide        (H.3.10), tolylfluanid (H.3.11);    -   guanidines and others: guanidine (H.4.1), dodine (H.4.2), dodine        free base (H.4.3), guazatine (H.4.4), guazatine-acetate (H.4.5),        iminoctadine (H.4.6), iminoctadine-triacetate (H.4.7),        iminoctadine-tris(albesilate) (H.4.8), dithianon (H.4.9),        2,6-dimethyl-1H,5H-[1,4]di-thiino[2,3-c:5,6-c′]dipyrrole-1,3,5,7(2H,6H)-tetraone        (H.4.10);

I) Cell Wall Synthesis Inhibitors

-   -   inhibitors of glucan synthesis: validamycin (1.1.1), polyoxin B        (1.1.2);    -   melanin synthesis inhibitors: pyroquilon (1.2.1), tricyclazole        (1.2.2), carpropamid (1.2.3), dicyclomet (1.2.4), fenoxanil        (1.2.5);

J) Plant Defence Inducers

-   -   acibenzolar-S-methyl (J.1.1), probenazole (J.1.2), isotianil        (J.1.3), tiadinil (J.1.4), prohexadione-calcium (J.1.5);        phosphonates: fosetyl (J.1.6), fosetyl-aluminum (J.1.7),        phosphorous acid and its salts (J.1.8), calcium phosphonate        (J.1.11), potassium phosphonate (J.1.12), potassium or sodium        bicarbonate (J.1.9),        4-cyclopropyl-N-(2,4-dimethoxy-phenyl)thiadiazole-5-carboxamide        (J.1.10);

K) Unknown Mode of Action

-   -   bronopol (K.1.1), chinomethionat (K.1.2), cyflufenamid (K.1.3),        cymoxanil (K.1.4), dazomet (K.1.5), debacarb (K.1.6), diclocymet        (K.1.7), diclomezine (K.1.8), difenzoquat (K.1.9),        difenzoquat-methylsulfate (K.1.10), diphenylamin (K.1.11),        fenitropan (K.1.12), fenpyrazamine (K.1.13), flumetover        (K.1.14), flusulfamide (K.1.15), flutianil (K.1.16), harpin        (K.1.17), methasulfocarb (K.1.18), nitrapyrin (K.1.19),        nitrothal-isopropyl (K.1.20), tolprocarb (K.1.21), oxin-copper        (K.1.22), proquinazid (K.1.23), tebufloquin (K.1.24),        tecloftalam (K.1.25), triazoxide (K.1.26),        N′-(4-(4-chloro-3-trifluoromethyl-phenoxy)-2,5-dimethyl-phenyl)-N-ethyl-N-methyl        formamidine (K.1.27),        N′-(4-(4-fluoro-3-trifluoromethyl-phenoxy)-2,5-dimethyl-phenyl)-N-ethyl-N-methyl        formamidine (K.1.28),        N′-[4-[[3-[(4-chlorophenyl)methyl]-1,2,4-thiadiazol-5-yl]oxy]-2,5-dimethyl-phenyl]-N-ethyl-N-methyl-formamidine        (K.1.29),        N′-(5-bromo-6-indan-2-yloxy-2-methyl-3-pyridyl)-N-ethyl-N-methyl-formamidine        (K.1.30),        N′-[5-bromo-6-[1-(3,5-difluorophenyl)ethoxy]-2-methyl-3-pyridyl]-N-ethyl-N-methyl-formamidine        (K.1.31),        N′-[5-bromo-6-(4-isopropylcyclohexoxy)-2-methyl-3-pyridyl]-N-ethyl-N-methyl-formamidine        (K.1.32),        N′-[5-bromo-2-methyl-6-(1-phenylethoxy)-3-pyridyl]-N-ethyl-N-methyl-formamidine        (K.1.33),        N′-(2-methyl-5-trifluoromethyl-4-(3-trimethylsilanyl-propoxy)-phenyl)-N-ethyl-N-methyl        formamidine (K.1.34),        N′-(5-difluoromethyl-2-methyl-4-(3-trimethylsilanyl-propoxy)-phenyl)-N-ethyl-N-methyl        formamidine (K.1.35),        2-(4-chloro-phenyl)-N-[4-(3,4-dimethoxy-phenyl)-isoxazol-5-yl]-2-prop-2-ynyloxy-acetamide        (K.1.36),        3-[5-(4-chloro-phenyl)-2,3-dimethyl-isoxazolidin-3-yl]-pyridine        (pyrisoxazole) (K.1.37),        3-[5-(4-methylphenyl)-2,3-dimethyl-isoxazolidin-3 yl]-pyridine        (K.1.38),        5-chloro-1-(4,6-dimethoxy-pyrimidin-2-yl)-2-methyl-1H-benzoimidazole        (K.1.39), ethyl (Z)-3-amino-2-cyano-3-phenyl-prop-2-enoate        (K.1.40), picarbutrazox (K.1.41), pentyl        N-[6-[[(Z)-[(1-methyltetrazol-5-yl)-phenyl-methylene]amino]oxymethyl]-2-pyridyl]carbamate        (K.1.42), but-3-ynyl        N-[6-[[(Z)-[(1-methyltetrazol-5-yl)-phenyl-methylene]amino]oxymethyl]-2-pyridyl]carbamate        (K.1.43),        2-[2-[(7,8-difluoro-2-methyl-3-quinolyl)oxy]-6-fluoro-phenyl]propan-2-ol        (K.1.44),        2-[2-fluoro-6-[(8-fluoro-2-methyl-3-quinolyl)oxy]phen-yl]propan-2-ol        (K.1.45), quinofumelin (K.1.47),        9-fluoro-2,2-dimethyl-5-(3-quinolyl)-3H-1,4-benzoxazepine        (K.1.49), 2-(6-benzyl-2-pyridyl)quinazoline (K.1.50),        2-[6-(3-fluoro-4-methoxy-phenyl)-5-methyl-2-pyridyl]quinazoline        (K.1.51), dichlobentiazox (K.1.52),        N′-(2,5-dimethyl-4-phenoxy-phenyl)-N-ethyl-N-methyl-formamidine        (K.1.53), pyrifenamine (K.1.54).

L) Biopesticides

L1) Microbial pesticides with fungicidal, bactericidal, viricidal and/orplant defense activator activity: Ampelomyces quisqualis, Aspergillusflavus, Aureobasidium pullulans, Bacillus altitudinis, B.amyloliquefaciens, B. megaterium, B. mojavensis, B. mycoides, B.pumilus, B. simplex, B. solisalsi, B. subtilis, B. subtilis var.amyloliquefaciens, Candida oleo-phila, C. saitoana, Clavibactermichiganensis (bacteriophages), Coniothyrium minitans, Cryphonectriaparasitica, Cryptococcus albidus, Dilophosphora alopecuri, Fusariumoxysporum, Clonostachys rosea f. catenulate (also named Gliocladiumcatenulatum), Gliocladium roseum, Lysobacter antibioticus, L.enzymogenes, Metschnikowia fructicola, Microdochium dimerum,Microsphaeropsis ochracea, Muscodor albus, PaeniBacillus alvei,PaeniBacillus epiphyticus, P. polymyxa, Pantoea vagans, Penicilliumbilaiae, Phlebiopsis gigantea, Pseudomonas sp., Pseudomonas chloraphis,Pseudozyma flocculosa, Pichia anomala, Pythium oligandrum, Sphaerodesmycoparasitica, Streptomyces griseoviridis, S. lydicus, S.violaceusniger, Talaromyces flavus, Trichoderma asperelloides, T.asperellum, T. atroviride, T. fertile, T. gamsii, T. harmatum, T.harzianum, T. polysporum, T. stromaticum, T. virens, T. viride, Typhulaphacorrhiza, Ulocladium oudemansii, Verticillium dahlia, zucchini yellowmosaic virus (avirulent strain);

L2) Biochemical pesticides with fungicidal, bactericidal, viricidaland/or plant defense activator activity: harpin protein, Reynoutriasachalinensis extract;

L3) Microbial pesticides with insecticidal, acaricidal, molluscidaland/or nematicidal activity: Agrobacterium radiobacter, Bacillus cereus,B. firmus, B. thuringiensis, B. thuringiensis ssp. aizawai, B. t. ssp.israelensis, B. t. ssp. galleriae, B. t. ssp. kurstaki, B. t. ssp.tenebrionis, Beauveria bassiana, B. brongniartii, Burkholderia spp.,Chromobacterium subtsugae, Cydia pomonella granulovirus (CpGV),Cryptophlebia leucotreta granulovirus (CrIeGV), Flavobacterium spp.,Helicoverpa armigera nucleopolyhedrovirus (HearNPV), Helicoverpa zeanucleopolyhedrovirus (HzNPV), Helicoverpa zea single capsidnucleopolyhedrovirus (HzSNPV), Heterorhabditis bacteriophora, Isariafumosorosea, Lecanicillium longisporum, L. muscarium, Metarhiziumanisopliae, M. anisopliae var. anisopliae, M. anisopliae var. acridum,Nomuraea rileyi, Paecilomyces fumosoroseus, P. lilacinus, PaeniBacilluspopilliae, Pasteuria spp., P. nishizawae, P. penetrans, P. ramosa, P.thornea, P. usgae, Pseudomonas fluorescens, Spodoptera littoralisnucleopolyhedrovirus (SpIiNPV), Steinernema carpocapsae, S. feltiae, S.kraussei, Streptomyces galbus, S. microflavus;

L4) Biochemical pesticides with insecticidal, acaricidal, molluscidal,pheromone and/or nematicidal activity: L-carvone, citral,(E,Z)-7,9-dodecadien-1-yl acetate, ethyl formate, (E,Z)-2,4-ethyldecadienoate (pear ester), (Z,Z,E)-7,11,13-hexadecatrienal, heptylbutyrate, isopropyl myristate, lavanulyl senecioate, cis-jasmone,2-methyl 1-butanol, methyl eugenol, methyl jasmonate,(E,Z)-2,13-octadecadien-1-ol, (E,Z)-2,13-octadecadien-1-ol acetate,(E,Z)-3,13-octadecadien-1-ol, (R)-1-octen-3-ol, pentatermanone,(E,Z,Z)-3,8,11-tetradecatrienyl acetate, (Z,E)-9,12-tetradecadien-1-ylacetate, (Z)-7-tetradecen-2-one, (Z)-9-tetradecen-1-yl acetate,(Z)-11-tetradecenal, (Z)-11-tetradecen-1-ol, extract of Chenopodiumambrosiodes, Neem oil, Quillay extract;

L5) Microbial pesticides with plant stress reducing, plant growthregulator, plant growth promoting and/or yield enhancing activity:Azospirillum amazonense, A. brasilense, A. lipoferum, A. irakense, A.halopraeferens, Bradyrhizobium spp., B. elkanii, B. japonicum, B.liaoningense, B. lupini, Delftia acidovorans, Glomus intraradices,Mesorhizobium spp., Rhizobium leguminosarum bv. phaseoli, R. I. bv.trifolii, R. I. bv. viciae, R. tropici, Sinorhizobium meliloti.

M) Insecticides

M.1) Acetylcholine esterase (AChE) inhibitors: M.1A carbamates, e.g.aldicarb, alanycarb, bendiocarb, benfuracarb, butocarboxim,butoxycarboxim, carbaryl, carbofuran, carbosulfan, ethiofencarb,fenobucarb, formetanate, furathiocarb, isoprocarb, methiocarb, methomyl,metolcarb, oxamyl, pirimicarb, propoxur, thiodicarb, thiofanox,trimethacarb, XMC, xylylcarb and triazamate; or M.1B organophosphates,e.g. acephate, azamethiphos, azinphos-ethyl, azinphosmethyl, cadusafos,chlorethoxyfos, chlorfenvinphos, chlormephos, chlorpyrifos,chlorpyrifos-methyl, coumaphos, cyanophos, demeton-S-methyl, diazinon,dichlorvos/DDVP, dicrotophos, dimethoate, dimethylvinphos, disulfoton,EPN, ethion, ethoprophos, famphur, fenamiphos, fenitrothion, fenthion,fosthiazate, heptenophos, imicyafos, isofenphos, isopropylO-(methoxyaminothio-phosphoryl) salicylate, isoxathion, malathion,mecarbam, methamidophos, methidathion, mevinphos, monocrotophos, naled,omethoate, oxydemeton-methyl, parathion, parathion-methyl, phenthoate,phorate, phosalone, phosmet, phosphamidon, phoxim, pirimiphos-methyl,profenofos, propetamphos, prothiofos, pyraclofos, pyridaphenthion,quinalphos, sulfotep, tebupirimfos, temephos, terbufos,tetrachlorvinphos, thiometon, triazophos, trichlorfon, and vamidothion;

M.2) GABA-gated chloride channel antagonists: M.2A cyclodieneorganochlorine compounds, e.g. endosulfan or chlordane; or M.2B fiproles(phenylpyrazoles), e.g. ethiprole, fipronil, flufiprole, pyrafluprole,and pyriprole;

M.3) Sodium channel modulators from the class of M.3A pyrethroids, e.g.acrinathrin, allethrin, d-cis-trans allethrin, d-trans allethrin,bifenthrin, kappa-bifenthrin, bioallethrin, bioallethrinS-cylclopentenyl, bioresmethrin, cycloprothrin, cyfluthrin,beta-cyfluthrin, cyhalothrin, lambda-cyhalothrin, gamma-cyhalothrin,cypermethrin, alpha-cypermethrin, beta-cypermethrin, theta-cypermethrin,zeta-cypermethrin, cyphenothrin, deltamethrin, empenthrin,esfenvalerate, etofenprox, fenpropathrin, fenvalerate, flucythrinate,flumethrin, tau-fluvalinate, halfenprox, heptafluthrin, imiprothrin,meperfluthrin, metofluthrin, momfluorothrin, epsilon-momfluorothrin,permethrin, phenothrin, prallethrin, profluthrin, pyrethrin (pyrethrum),resmethrin, silafluofen, tefluthrin, kappa-tefluthrin,tetramethylfluthrin, tetramethrin, tralomethrin, and transfluthrin; orM.3B sodium channel modulators such as DDT or methoxychlor;

M.4) Nicotinic acetylcholine receptor agonists (nAChR): M.4Aneonicotinoids, e.g. acetamiprid, clothianidin, cycloxaprid,dinotefuran, imidacloprid, nitenpyram, thiacloprid and thiamethoxam; orthe compounds M.4A.14,5-Dihydro-N-nitro-1-(2-oxiranylmethyl)-1H-imidazol-2-amine, M.4A.2:(2E−)-1-[(6-Chloropyridin-3-yl)methyl]-N′-nitro-2-pentylidenehydrazinecarboximidamide;or M4.A.3:1-[(6-Chloropyridin-3-yl)methyl]-7-methyl-8-nitro-5-propoxy-1,2,3,5,6,7-hexahydroimidazo[1,2-a]pyridine;or M.4B nicotine; M.4C sulfoxaflor; M.4D flupyradifurone; M.4Etriflumezopyrim;

M.5) Nicotinic acetylcholine receptor allosteric activators:spinosyns,e.g. spinosad or spinetoram;

M.6) Chloride channel activators from the class of avermectins andmilbemycins, e.g. abamectin, emamectin benzoate, ivermectin, lepimectin,or milbemectin;

M.7) Juvenile hormone mimics, such as M.7A juvenile hormone analogueshydroprene, kinoprene, and methoprene; or M.7B fenoxycarb, or M.7Cpyriproxyfen;

M.8) miscellaneous non-specific (multi-site) inhibitors, e.g. M.8A alkylhalides as methyl bromide and other alkyl halides, M.8B chloropicrin,M.8C sulfuryl fluoride, M.8D borax, or M.8E tartar emetic;

M.9) Chordotonal organ TRPV channel modulators, e.g. M.9B pymetrozine;pyrifluquinazon;

-   -   M.10 Mite growth inhibitors, e.g. M.10A clofentezine,        hexythiazox, and diflovidazin, or M.10B etoxazole;

M.10) Mite growth inhibitors, e.g. M.10A clofentezine, hexythiazox, anddiflovidazin, or M.10B etoxazole;

M.11) Microbial disruptors of insect midgut membranes, e.g. Bacillusthuringiensis or Bacillus sphaericus and the insecticidal proteins theyproduce such as Bacillus thuringiensis subsp. israelensis, Bacillussphaericus, Bacillus thuringiensis subsp. aizawai, Bacillusthuringiensis subsp. kurstaki and Bacillus thuringiensis subsp.tenebrionis, or the Bt crop proteins: Cry1Ab, Cry1Ac, Cry1Fa, Cry2Ab,mCry3A, Cry3Ab, Cry3Bb, and Cry34/35Ab1;

M.12) Inhibitors of mitochondrial ATP synthase, e.g. M.12Adiafenthiuron, or M.12B organotin miticides such as azocyclotin,cyhexatin, or fenbutatin oxide, M.12C propargite, or M.12D tetradifon;

M.13) Uncouplers of oxidative phosphorylation via disruption of theproton gradient, e.g. chlorfenapyr, DNOC, or sulfluramid;

M.14) Nicotinic acetylcholine receptor (nAChR) channel blockers, e.g.nereistoxin analogues bensultap, cartap hydrochloride, thiocyclam, orthiosultap sodium;

M.15) Inhibitors of the chitin biosynthesis type 0, such as benzoylurease.g. bistrifluron, chlorfluazuron, diflubenzuron, flucycloxuron,flufenoxuron, hexaflumuron, lufenuron, novaluron, noviflumuron,teflubenzuron, or triflumuron;

M.16) Inhibitors of the chitin biosynthesis type 1, e.g. buprofezin;

M.17) Moulting disruptors, Dipteran, e.g. cyromazine;

M.18) Ecdyson receptor agonists such as diacylhydrazines, e.g.methoxyfenozide, tebufenozide, halofenozide, fufenozide, orchromafenozide;

M.19) Octopamin receptor agonists, e.g. amitraz;

M.20) Mitochondrial complex III electron transport inhibitors, e.g.M.20A hydramethylnon,

-   -   M.20B acequinocyl. M.20C fluacrypyrim; or M.20D bifenazate;

M.21) Mitochondrial complex I electron transport inhibitors, e.g. M.21AMETI acaricides and insecticides such as fenazaquin, fenpyroximate,pyrimidifen, pyridaben, tebufenpyrad or tolfenpyrad, or M.21B rotenone;

M.22) Voltage-dependent sodium channel blockers, e.g. M.22A indoxacarb,M.22B metaflumizone, or M.22B.1:2-[2-(4-Cyanophenyl)-1-[3-(trifluoromethyl)phenyl]-ethylidene]-N-[4-(difluoromethoxy)phenyl]-hydrazinecarboxamideor M.22B.2: N-(3-Chloro-2-methylphenyl)-2-[(4-chlorophenyl)[4-[methyl(methylsulfonyl)amino]phenyl]methylene]-hydrazinecarboxamide;

M.23) Inhibitors of the of acetyl CoA carboxylase, such as Tetronic andTetramic acid derivatives, e.g. spirodiclofen, spiromesifen, orspirotetramat; M.23.1 spiropidion;

M.24) Mitochondrial complex IV electron transport inhibitors, e.g. M.24Aphosphine such as aluminium phosphide, calcium phosphide, phosphine orzinc phosphide, or M.24B cyanide;

M.25) Mitochondrial complex II electron transport inhibitors, such asbeta-ketonitrile derivatives, e.g. cyenopyrafen or cyflumetofen;

M.28) Ryanodine receptor-modulators from the class of diamides, e.g.flubendiamide, chlorantraniliprole, cyantraniliprole, tetraniliprole,M.28.1:(R)-3-Chlor-N1-{2-methyl-4-[1,2,2,2-tetrafluoro-1-(trifluoromethyl)ethyl]phenyl}-N2-(1-methyl-2-methylsulfonylethyl)phthalamid,M.28.2:(S)-3-Chloro-N1-{2-methyl-4-[1,2,2,2-tetrafluoro-1-(trifluoromethyl)ethyl]phenyl}-N2-(1-methyl-2-methylsulfonylethyl)phthalamid,M.28.3: cyclaniliprole, or M.28.4:methyl-2-[3,5-dibromo-2-({[3-bromo-1-(3-chlorpyridin-2-yl)-1H-pyrazol-5-yl]carbonyl}-amino)benzoyl]-1,2-dimethylhydrazinecarboxylate;or M.28.5a)N-[4,6-dichloro-2-[(diethyl-lambda-4-sulfanylidene)carbamoyl]-phenyl]-2-(3-chloro-2-pyridyl)-5-(trifluoromethyl)pyrazole-3-carboxamide;M.28.5b)N-[4-chloro-2-[(diethyl-lambda-4-sulfanylidene)carbamoyl]-6-methyl-phenyl]-2-(3-chloro-2-pyridyl)-5-(trifluoromethyl)pyrazole-3-carboxamide;M.28.5c)N-[4-chloro-2-[(di-2-propyl-lambda-4-sulfanylidene)carbamoyl]-6-methyl-phenyl]-2-(3-chloro-2-pyridyl)-5-(trifluoromethyl)pyrazole-3-carboxamide;M.28.5d)N-[4,6-dichloro-2-[(di-2-propyl-lambda-4-sulfanylidene)carbamoyl]-phenyl]-2-(3-chloro-2-pyridyl)-5-(trifluoro-methyl)pyrazole-3-carboxamide;M.28.5h)N-[4,6-dibromo-2-[(diethyl-lambda-4-sulfanylidene)carbamoyl]-phenyl]-2-(3-chloro-2-pyridyl)-5-(trifluoromethyl)pyrazole-3-carboxamide;M.28.5i)N-[2-(5-Amino-1,3,4-thiadiazol-2-yl)-4-chloro-6-methylphenyl]-3-bromo-1-(3-chloro-2-pyridinyl)-1H-pyrazole-5-carboxamide;M.28.5j)3-Chloro-1-(3-chloro-2-pyridinyl)-N-[2,4-dichloro-6-[[(1-cyano-1-methylethyl)amino]carbonyl]phenyl]-1H-pyrazole-5-carboxamide;M.28.5k)3-Bromo-N-[2,4-dichloro-6-(methylcarbamoyl)phenyl]-1-(3,5-dichloro-2-pyridyl)-1H-pyrazole-5-carboxamide;M.28.51)N-[4-Chloro-2-[[(1,1-dimethylethyl)amino]carbonyl]-6-methylphenyl]-1-(3-chloro-2-pyridinyl)-3-(fluoromethoxy)-1H-pyrazole-5-carboxamide;or M.28.6: cyhalodiamide; or

M.29) Chordotonal organ Modulators—undefined target site, e.g.flonicamid;

M.UN. insecticidal active compounds of unknown or uncertain mode ofaction, e.g. afidopyropen, afoxolaner, azadirachtin, amidoflumet,benzoximate, broflanilide, bromopropylate, chinomethionat, cryolite,dicloromezotiaz, dicofol, flufenerim, flometoquin, fluensulfone,fluhexafon, fluopyram, fluralaner, metaldehyde, metoxadiazone, piperonylbutoxide, pyflubumide, pyridalyl, tioxazafen, M.UN.3:11-(4-chloro-2,6-dimethylphenyl)-12-hydroxy-1,4-dioxa-9-azadispiro[4.2.4.2]-tetradec-11-en-10-one,

M.UN.4:3-(4′-fluoro-2,4-dimethylbiphenyl-3-yl)-4-hydroxy-8-oxa-1-azaspiro[4.5]dec-3-en-2-one,

M.UN.5:1-[2-fluoro-4-methyl-5-[(2,2,2-trifluoroethyl)sulfinyl]phenyl]-3-(trifluoromethyl)-1H-1,2,4-triazole-5-amine,or actives on basis of Bacillus firmus (Votivo, 1-1582);

M.UN.6: flupyrimin;

M.UN.8: fluazaindolizine; M.UN.9.a):4-[5-(3,5-dichlorophenyl)-5-(trifluoromethyl)-4H-isoxazol-3-yl]-2-methyl-N-(1-oxothietan-3-yl)benzamide;M.UN.9.b): fluxametamide; M.UN.10:5-[3-[2,6-dichloro-4-(3,3-dichloroallyloxy)phenoxy]propoxy]-1H-pyrazole;M.UN.11.i)4-cyano-N-[2-cyano-5-[[2,6-dibromo-4-[1,2,2,3,3,3-hexafluoro-1-(trifluoromethyl)propyl]phenyl]carbamoyl]phenyl]-2-methyl-benzamide;M.UN.11.j)4-cyano-3-[(4-cyano-2-methyl-benzoyl)amino]-N-[2,6-dichloro-4-[1,2,2,3,3,3-hexafluoro-1-(trifluoromethyl)propyl]phenyl]-2-fluoro-benzamide;M.UN.11.k)N-[5-[[2-chloro-6-cyano-4-[1,2,2,3,3,3-hexafluoro-1-(trifluoromethyl)propyl]phenyl]carbamoyl]-2-cyano-phenyl]-4-cyano-2-methyl-benzamide;M.UN.11.1)N-[5-[[2-bromo-6-chloro-4-[2,2,2-trifluoro-1-hydroxy-1-(trifluoromethyl)ethyl]phenyl]carbamoyl]-2-cyano-phenyl]-4-cyano-2-methyl-benzamide;M.UN.11.m)N-[5-[[2-bromo-6-chloro-4-[1,2,2,3,3,3-hexafluoro-1-(trifluoromethyl)propyl]phenyl]carbamoyl]-2-cyano-phenyl]-4-cyano-2-methyl-benzamide;M.UN.11.n)4-cyano-N-[2-cyano-5-[[2,6-dichloro-4-[1,2,2,3,3,3-hexafluoro-1-(trifluoromethyl)propyl]phenyl]carbamoyl]phenyl]-2-methyl-benzamide;M.UN.11.o)4-cyano-N-[2-cyano-5-[[2,6-dichloro-4-[1,2,2,2-tetrafluoro-1-(trifluoromethyl)ethyl]phenyl]carbamoyl]phenyl]-2-methyl-benzamide;M.UN.11.p)N-[5-[[2-bromo-6-chloro-4-[1,2,2,2-tetrafluoro-1-(trifluoromethyl)ethyl]phenyl]carbamoyl]-2-cyano-phenyl]-4-cyano-2-methyl-benzamide;or

M.UN.12.a) 2-(1,3-Dioxan-2-yl)-6-[2-(3-pyridinyl)-5-thiazolyl]-pyridine;M.UN.12.b)2-[6-[2-(5-Fluoro-3-pyridinyl)-5-thiazolyl]-2-pyridinyl]-pyrimidine;M.UN.12.c) 2-[6-[2-(3-Pyridinyl)-5-thiazolyl]-2-pyridinyl]-pyrimidine;M.UN.12.d)N-Methylsulfonyl-6-[2-(3-pyridyl)thiazol-5-yl]pyridine-2-carboxamide;M.UN.12.e)N-Methylsulfonyl-6-[2-(3-pyridyl)thiazol-5-yl]pyridine-2-carboxamide;

M.UN.14a)1-[(6-Chloro-3-pyridinyl)methyl]-1,2,3,5,6,7-hexahydro-5-methoxy-7-methyl-8-nitro-imidazo[1,2-a]pyridine;or M.UN.14b)1-[(6-Chloropyridin-3-yl)methyl]-7-methyl-8-nitro-1,2,3,5,6,7-hexahydroimidazo[1,2-a]pyridin-5-ol;

M.UN.16a)1-isopropyl-N,5-dimethyl-N-pyridazin-4-yl-pyrazole-4-carboxamide; orM.UN.16b)1-(1,2-dimethylpropyl)-N-ethyl-5-methyl-N-pyridazin-4-yl-pyrazole-4-carboxamide;M.UN.16c)N,5-dimethyl-N-pyridazin-4-yl-1-(2,2,2-trifluoro-1-methylethyl)pyrazole-4-carboxamide; M.UN.16d)1-[1-(1-cyanocyclopropyl)ethyl]-N-ethyl-5-methyl-N-pyridazin-4-yl-pyrazole-4-carboxamide;M.UN.16e)N-ethyl-1-(2-fluoro-1-methyl-propyl)-5-methyl-N-pyridazin-4-yl-pyrazole-4-carboxamide;M.UN.16f)1-(1,2-dimethylpropyl)-N,5-dimethyl-N-pyridazin-4-yl-pyrazole-4-carboxamide;M.UN.16g)1-[1-(1-cyanocyclopropyl)ethyl]-N,5-dimethyl-N-pyridazin-4-yl-pyrazole-4-carboxamide;M.UN.16h)N-methyl-1-(2-fluoro-1-methyl-propyl]-5-methyl-N-pyridazin-4-yl-pyrazole-4-carboxamide;M.UN.16i)1-(4,4-difluorocyclohexyl)-N-ethyl-5-methyl-N-pyridazin-4-yl-pyrazole-4-carboxamide;or M.UN.16j)1-(4,4-difluorocyclohexyl)-N,5-dimethyl-N-pyridazin-4-yl-pyrazole-4-carboxamide,

M.UN.17a) N-(1-methylethyl)-2-(3-pyridinyl)-2H-indazole-4-carboxamide;M.UN.17b) N-cyclopropyl-2-(3-pyridinyl)-2H-indazole-4-carboxamide;M.UN.17c) N-cyclohexyl-2-(3-pyridinyl)-2H-indazole-4-carboxamide;M.UN.17d)2-(3-pyridinyl)-N-(2,2,2-trifluoroethyl)-2H-indazole-4-carboxamide;M.UN.17e)2-(3-pyridinyl)-N-[(tetrahydro-2-furanyl)methyl]-2H-indazole-5-carboxamide;M.UN.17f) methyl2-[[2-(3-pyridinyl)-2H-indazol-5-yl]carbonyl]hydrazinecarboxylate;M.UN.17g)N-[(2,2-difluorocyclopropyl)methyl]-2-(3-pyridinyl)-2H-indazole-5-carboxamide;M.UN.17h)N-(2,2-difluoropropyl)-2-(3-pyridinyl)-2H-indazole-5-carboxamide;M.UN.17i)2-(3-pyridinyl)-N-(2-pyrimidinylmethyl)-2H-indazole-5-carboxamide;M.UN.17j)N-[(5-methyl-2-pyrazinyl)methyl]-2-(3-pyridinyl)-2H-indazole-5-carboxamide,

M.UN.18. tyclopyrazoflor;

M.UN.19 sarolaner, M.UN.20 lotilaner;

M.UN.21N-[4-Chloro-3-[[(phenylmethyl)amino]carbonyl]phenyl]-1-methyl-3-(1,1,2,2,2-pentafluoroethyl)-4-(trifluoromethyl)-1H-pyrazole-5-carboxamide;M.UN.22a2-(3-ethylsulfonyl-2-pyridyl)-3-methyl-6-(trifluoromethyl)imidazo[4,5-b]pyridine,or M.UN.22b2-[3-ethylsulfonyl-5-(trifluoromethyl)-2-pyridyl]-3-methyl-6-(trifluoromethyl)imidazo[4,5-b]pyridine;

M.UN.23a)4-[5-(3,5-dichlorophenyl)-5-(trifluoromethyl)-4H-isoxazol-3-yl]-N-[(4R)-2-ethyl-3-oxo-isoxazolidin-4-yl]-2-methyl-benzamide,or M.UN.23b)4-[5-(3,5-dichloro-4-fluoro-phenyl)-5-(trifluoromethyl)-4H-isoxazol-3-yl]-N-[(4R)-2-ethyl-3-oxo-isoxazolidin-4-yl]-2-methyl-benzamide;

M.UN.24a)N-[4-chloro-3-(cyclopropylcarbamoyl)phenyl]-2-methyl-5-(1,1,2,2,2-pentafluoroethyl)-4-(trifluoromethyl)pyrazole-3-carboxamideor M.UN.24b)N-[4-chloro-3-[(1-cyanocyclopropyl)carbamoyl]phenyl]-2-methyl-5-(1,1,2,2,2-pentafluoroethyl)-4-(trifluoromethyl)pyrazole-3-carboxamide;M.UN.25 acynonapyr; M.UN.26 benzpyrimoxan; M.UN.272-chloro-N-(1-cyanocyclopropyl)-5-[1-[2-methyl-5-(1,1,2,2,2-pentafluoroethyl)-4-(trifluoromethyl)pyrazol-3-yl]pyrazol-4-yl]benzamide; M.UN.28 Oxazosulfyl;

M.UN.29a)[(2S,3R,4R,5S,6S)-3,5-dimethoxy-6-methyl-4-propoxy-tetrahydropyran-2-yl]N-[4-[1-[4-(trifluoromethoxy)phenyl]-1,2,4-triazol-3-yl]phenyl]carbamate; M.UN.29b)[(2S,3R,4R,5S,6S)-3,4,5-trimethoxy-6-methyl-tetrahydropyran-2-yl]N-[4-[1-[4-(trifluoromethoxy)phenyl]-1,2,4-triazol-3-yl]phenyl]carbamate;M.UN.29c)[(2S,3R,4R,5S,6S)-3,5-dimethoxy-6-methyl-4-propoxy-tetrahydropyran-2-yl]N-[4-[1-[4-(1,1,2,2,2-pentafluoroethoxy)phenyl]-1,2,4-triazol-3-yl]phenyl]carbamate;M.UN.29d)[(2S,3R,4R,5S,6S)-3,4,5-trimethoxy-6-methyl-tetrahydropyran-2-yl]N-[4-[1-[4-(1,1,2,2,2-pentafluoroethoxy)phenyl]-1,2,4-triazol-3-yl]phenyl]carbamate;M.UN.29.e)(2Z)-3-(2-isopropylphenyl)-2-[(E)-[4-[1-[4-(trifluoromethoxy)phenyl]-1,2,4-triazol-3-yl]phenyl]methylenehydrazono]thiazolidin-4-oneor M.UN.29f)(2Z)-3-(2-isopropylphenyl)-2-[(E)-[4-[1-[4-(1,1,2,2,2-pentafluoroethoxy)phenyl]-1,2,4-triazol-3-yl]phenyl]methylenehydrazono]thiazolidin-4-one.

N) Herbicides

-   -   herbicides from the classes of the acetamides, amides,        aryloxyphenoxypropionates, benzamides, benzofuran, benzoic        acids, benzothiadiazinones, bipyridylium, carbamates,        chloroacetamides, chlorocarboxylic acids, cyclohexanediones,        dinitroanilines, dinitrophenol, diphenyl ether, glycines,        imidazolinones, isoxazoles, isoxazolidinones, nitriles,        N-phenylphthalimides, oxadiazoles, oxazolidinediones,        oxyacetamides, phenoxycarboxylic acids, phenylcarbamates,        phenylpyrazoles, phenylpyrazolines, phenylpyridazines,        phosphinic acids, phosphoroamidates, phosphorodithioates,        phthalamates, pyrazoles, pyridazinones, pyridines,        pyridinecarboxylic acids, pyridinecarboxamides,        pyrimidinediones, pyrimidinyl(thio)benzoates,        quinolinecarboxylic acids, semicarbazones,        sulfonylaminocarbonyltriazolinones, sulfonylureas,        tetrazolinones, thiadiazoles, thiocarbamates, triazines,        triazinones, triazoles, triazolinones, triazolocarboxamides,        triazolopyrimidines, triketones, uracils, or ureas.

The present invention furthermore relates to agrochemical compositionscomprising a mixture of at least one compound of formula I, i.e. anitrification inhibitor of the present invention (compound I orcomponent I) and at least one further active substance useful for plantprotection, e.g. selected from the groups A) to N) (component 2), inparticular one further herbicide selected from the group N).

By applying compounds I together with at least one active substance fromgroups A) to N) a synergistic plant health effect can be obtained, i.e.more than simple addition of the individual effects is obtained(synergistic mixtures).

This can be obtained by applying the compounds I and at least onefurther active substance simultaneously, either jointly (e.g. astank-mix) or separately, or in succession, wherein the time intervalbetween the individual applications is selected to ensure that theactive substance applied first still occurs at the site of action in asufficient amount at the time of application of the further activesubstance(s). The order of application is not essential for working ofthe present invention.

When applying compound I and a pesticide I sequentially the time betweenboth applications may vary e.g. between 2 hours to 7 days. Also abroader range is possible ranging from 0.25 hour to 30 days, preferablyfrom 0.5 hour to 14 days, particularly from 1 hour to 7 days or from 1.5hours to 5 days, even more preferred from 2 hours to 1 day. In case of amixture comprising a pesticide II selected from group L), it ispreferred that the pesticide I is applied as last treatment.

According to the invention, the solid material (dry matter) of thebiopesticides (with the exception of oils such as Neem oil, Tagetes oil,etc.) are considered as active components (e.g. to be obtained afterdrying or evaporation of the extraction medium or the suspension mediumin case of liquid formulations of the microbial pesticides).

In accordance with the present invention, the weight ratios andpercentages used herein for a biological extract such as Quillay extractare based on the total weight of the dry content (solid material) of therespective extract(s).

The total weight ratios of compositions comprising at least onemicrobial pesticide in the form of viable microbial cells includingdormant forms, can be determined using the amount of CFU of therespective microorganism to calculate the total weight of the respectiveactive component with the following equation that 1×10¹⁰ CFU equals onegram of total weight of the respective active component. Colony formingunit is measure of viable microbial cells, in particular fungal andbacterial cells. In addition, here “CFU” may also be understood as thenumber of (juvenile) individual nematodes in case of (entomopathogenic)nematode biopesticides, such as Steinernema feltiae.

In the binary mixtures and compositions according to the invention theweight ratio of the component 1) and the component 2) generally dependsfrom the properties of the active components used, usually it is in therange of from 1:100 to 100:1, regularly in the range of from 1:50 to50:1, preferably in the range of from 1:20 to 20:1, more preferably inthe range of from 1:10 to 10:1, even more preferably in the range offrom 1:4 to 4:1 and in particular in the range of from 1:2 to 2:1.

According to further embodiments of the binary mixtures andcompositions, the weight ratio of the component 1) and the component 2)usually is in the range of from 1000:1 to 1:1, often in the range offrom 100:1 to 1:1, regularly in the range of from 50:1 to 1:1,preferably in the range of from 20:1 to 1:1, more preferably in therange of from 10:1 to 1:1, even more preferably in the range of from 4:1to 1:1 and in particular in the range of from 2:1 to 1:1.

According to a further embodiments of the binary mixtures andcompositions, the weight ratio of the component 1) and the component 2)usually is in the range of from 1:1 to 1:1000, often in the range offrom 1:1 to 1:100, regularly in the range of from 1:1 to 1:50,preferably in the range of from 1:1 to 1:20, more preferably in therange of from 1:1 to 1:10, even more preferably in the range of from 1:1to 1:4 and in particular in the range of from 1:1 to 1:2.

According to further embodiments of the mixtures and compositions, theweight ratio of the component 1) and the component 2) generally dependsfrom the properties of the active components used, usually it is in therange of from 1:10,000 to 10,000:1, regularly in the range of from 1:100to 10,000:1, preferably in the range of from 1:100 to 5,000:1, morepreferably in the range of from 1:1 to 1,000:1, even more preferably inthe range of from 1:1 to 500:1 and in particular in the range of from10:1 to 300:1.

According to further embodiments of the mixtures and compositions, theweight ratio of the component 1) and the component 2) usually is in therange of from 20,000:1 to 1:10, often in the range of from 10,000:1 to1:1, regularly in the range of from 5,000:1 to 5:1, preferably in therange of from 5,000:1 to 10:1, more preferably in the range of from2,000:1 to 30:1, even more preferably in the range of from 2,000:1 to100:1 and in particular in the range of from 1,000:1 to 100:1.

According to further embodiments of the mixtures and compositions, theweight ratio of the component 1) and the component 2) usually is in therange of from 1:20,000 to 10:1, often in the range of from 1:10,000 to1:1, regularly in the range of from 1:5,000 to 1:5, preferably in therange of from 1:5,000 to 1:10, more preferably in the range of from1:2,000 to 1:30, even more preferably in the range of from 1:2,000 to1:100 and in particular in the range of from 1:1,000 to 1:100.

In the ternary mixtures, i.e. compositions according to the inventioncomprising the component 1) and component 2) and a compound III(component 3), the weight ratio of component 1) and component 2) dependsfrom the properties of the active substances used, usually it is in therange of from 1:100 to 100:1, regularly in the range of from 1:50 to50:1, preferably in the range of from 1:20 to 20:1, more preferably inthe range of from 1:10 to 10:1 and in particular in the range of from1:4 to 4:1, and the weight ratio of component 1) and component 3)usually it is in the range of from 1:100 to 100:1, regularly in therange of from 1:50 to 50:1, preferably in the range of from 1:20 to20:1, more preferably in the range of from 1:10 to 10:1 and inparticular in the range of from 1:4 to 4:1.

Any further active components are, if desired, added in a ratio of from20:1 to 1:20 to the component 1).

These ratios are also suitable for inventive mixtures applied by seedtreatment.

The active substances listed under groups A) to K), their preparationand their activity e.g. against harmful fungi is known (cf.:http://www.alanwood.net/pesticides/); these substances are commerciallyavailable. The compounds described by IUPAC nomenclature, theirpreparation and their pesticidal activity are also known (cf. Can. J.Plant Sci. 48(6), 587-94, 1968; EP-A 141 317; EP-A 152 031; EP-A 226917; EP-A 243 970; EP-A 256 503; EP-A 428 941; EP-A 532 022; EP-A 1 028125; EP-A 1 035 122; EP-A 1 201 648; EP-A 1122 244, JP 2002316902; DE19650197; DE 10021412; DE 102005009458; U.S. Pat. Nos. 3,296,272;3,325,503; WO 98/46608; WO 99/14187; WO 99/24413; WO 99/27783; WO00/29404; WO 00/46148; WO 00/65913; WO 01/54501; WO 01/56358; WO02/22583; WO 02/40431; WO 03/10149; WO 03/11853; WO 03/14103; WO03/16286; WO 03/53145; WO 03/61388; WO 03/66609; WO 03/74491; WO04/49804; WO 04/83193; WO 05/120234; WO 05/123689; WO 05/123690; WO05/63721; WO 05/87772; WO 05/87773; WO 06/15866; WO 06/87325; WO06/87343; WO 07/82098; WO 07/90624, WO 10/139271, WO 11/028657, WO12/168188, WO 07/006670, WO 11/77514; WO 13/047749, WO 10/069882, WO13/047441, WO 03/16303, WO 09/90181, WO 13/007767, WO 13/010862, WO13/127704, WO 13/024009, WO 13/24010, WO 13/047441, WO 13/162072, WO13/092224, WO 11/135833, CN 1907024, CN 1456054, CN 103387541, CN1309897, WO 12/84812, CN 1907024, WO 09094442, WO 14/60177, WO13/116251, WO 08/013622, WO 15/65922, WO 94/01546, EP 2865265, WO07/129454, WO 12/165511, WO 11/081174, WO 13/47441).

Some compounds are identified by their CAS Registry Number which isseparated by hyphens into three parts, the first consisting from two upto seven digits, the second consisting of two digits, and the thirdconsisting of a single digit.

The commercially available compounds of the group M listed above may befound in The Pesticide Manual, 17th Edition, C. MacBean, British CropProtection Council (2015) among other publications. The online PesticideManual is updated regularly and is accessible throughhttp://bcpcdata.com/pesticide-manual.html.

Another online data base for pesticides providing the ISO common namesis http://www.alanwood.net/pesticides.

The M.4 cycloxaprid is known from WO2010/069266 and WO2011/069456.M.4A.1 is known from CN 103814937; CN105367557, CN 105481839. M.4A.2,guadipyr, is known from WO 2013/003977, and M.4A.3 (approved aspaichongding in China) is known from WO 2007/101369. M.22B.1 isdescribed in CN10171577 and M.22B.2 in CN102126994. Spiropidion M.23.1is known from WO 2014/191271. M.28.1 and M.28.2 are known fromWO2007/101540. M.28.3 is described in WO2005/077934. M.28.4 is describedin WO2007/043677. M.28.5a) to M.28.5d) and M.28.5h) are described in WO2007/006670, WO2013/024009 and WO 2013/024010, M.28.5i) is described inWO2011/085575, M.28.5j) in WO2008/134969, M.28.5k) in US2011/046186 andM.28.51) in WO2012/034403. M.28.6 can be found in WO2012/034472. M.UN.3is known from WO2006/089633 and M.UN.4 from WO2008/067911. M.UN.5 isdescribed in WO2006/043635, and biological control agents on the basisof Bacillus firmus are described in WO2009/124707. Flupyrimin isdescribed in WO2012/029672. M.UN.8 is known from WO2013/055584.M.UN.9.a) is described in WO2013/050317. M.UN.9.b) is described inWO2014/126208. M.UN.10 is known from WO2010/060379. Broflanilide andM.UN.11.b) to M.UN.11.h) are described in WO2010/018714, and M.UN.11i)to M.UN.11.p) in WO 2010/127926. M.UN.12.a) to M.UN.12.c) are known fromWO2010/006713, M.UN.12.d) and M.UN.12.e) are known from WO2012/000896.M.UN.14a) and M.UN.14b) are known from WO2007/101369. M.UN.16.a) toM.UN.16h) are described in WO2010/034737, WO2012/084670, andWO2012/143317, resp., and M.UN.16i) and M.UN.16j) are described inWO2015/055497. M.UN.17a) to M.UN.17.j) are described in WO2015/038503.M.UN.18 Tycloprazoflor is described in US2014/0213448. M.UN.19 isdescribed in WO2014/036056. M.UN.20 is known from WO2014/090918. M.UN.21is known from EP2910126. M.UN.22a and M.UN.22b are known fromWO2015/059039 and WO2015/190316. M.UN.23a and M.UN.23b are known fromWO2013/050302. M.UN.24a) and M.UN.24b) are known from WO2012/126766.Acynonapyr M.UN.25 is known from WO 2011/105506. Benzpyrimoxan M.UN.26is known from WO2016/104516. M.UN.27 is known from WO2016/174049.M.UN.28 Oxazosulfyl is known from WO2017/104592. M.UN.29a) to M.UN.29f)are known from WO2009/102736 or WO2013116053.

The biopesticides from group L1) and/or L2) may also have insecticidal,acaricidal, molluscidal, pheromone, nematicidal, plant stress reducing,plant growth regulator, plant growth promoting and/or yield enhancingactivity. The biopesticides from group L3) and/or L4) may also havefungicidal, bactericidal, viricidal, plant defense activator, plantstress reducing, plant growth regulator, plant growth promoting and/oryield enhancing activity.

The biopesticides from group L5) may also have fungicidal, bactericidal,viricidal, plant defense activator, insecticidal, acaricidal,molluscidal, pheromone and/or nematicidal activity.

Many of these biopesticides have been deposited under deposition numbersmentioned herein (the prefices such as ATCC or DSM refer to the acronymof the respective culture collection, for details see e.g. here:http://www.wfcc.info/ccinfo/collection/by_acronym/), are referred to inliterature, registered and/or are commercially available: mixtures ofAureobasidium pullulans DSM 14940 and DSM 14941 isolated in 1989 inKonstanz, Germany (e.g. blastospores in BlossomProtect® from bio-fermGmbH, Austria), Azospirillum brasilense Sp245 originally isolated inwheat region of South Brazil (Passo Fundo) at least prior to 1980 (BR11005; e.g. GELFIX® Gramineas from BASF Agricultural Specialties Ltd.,Brazil), A. brasilense strains Ab-V5 and Ab-V6 (e.g. in AzoMax fromNovozymes BioAg Produtos papra Agricultura Ltda., Quattro Barras, Brazilor Simbiose-Maiz® from Simbiose-Agro, Brazil; Plant Soil 331, 413-425,2010), Bacillus amyloliquefaciens strain AP-188 (NRRL B-50615 andB-50331; U.S. Pat. No. 8,445,255); B. amyloliquefaciens spp. plantarumD747 isolated from air in Kikugawa-shi, Japan (US 20130236522 A1; FERMBP-8234; e.g. Double Nickel™ 55 WDG from Certis LLC, USA), B.amyloliquefaciens spp. plantarum FZB24 isolated from soil inBrandenburg, Germany (also called SB3615; DSM 96-2; J. Plant Dis. Prot.105, 181-197, 1998; e.g. Taegro® from Novozyme Biologicals, Inc., USA),B. amyloliquefaciens ssp. plantarum FZB42 isolated from soil inBrandenburg, Germany (DSM 23117; J. Plant Dis. Prot. 105, 181-197, 1998;e.g. RhizoVital® 42 from AbiTEP GmbH, Germany), B. amyloliquefaciensssp. plantarum MB1600 isolated from faba bean in Sutton Bonington,Nottinghamshire, U.K. at least before 1988 (also called 1430; NRRLB-50595; US 2012/0149571 A1; e.g. Integral® from BASF Corp., USA), B.amyloliquefaciens spp. plantarum QST-713 isolated from peach orchard in1995 in California, U.S.A. (NRRL B-21661; e.g. Serenade® MAX from BayerCrop Science LP, USA), B. amyloliquefaciens spp. plantarum TJ1000isolated in 1992 in South Dakoda, U.S.A. (also called 1BE; ATCC BAA-390;CA 2471555 A1; e.g. QuickRoots™ from TJ Technologies, Watertown, S.Dak., USA), B. firmus CNCM 1-1582, a variant of parental strain EIP-N1(CNCM 1-1556) isolated from soil of central plain area of Israel (WO2009/126473, U.S. Pat. No. 6,406,690; e.g. Votivo® from BayerCropScience LP, USA), B. pumilus GHA 180 isolated from apple treerhizosphere in Mexico (IDAC 260707-01; e.g. PRO-MIX® BX from PremierHorticulture, Quebec, Canada), B. pumilus INR-7 otherwise referred to asBU-F22 and BU-F33 isolated at least before 1993 from cucumber infestedby Erwinia tracheiphila (NRRL B-50185, NRRL B-50153; U.S. Pat. No.8,445,255), B. pumilus KFP9F isolated from the rhizosphere of grasses inSouth Africa at least before 2008 (NRRL B-50754; WO 2014/029697; e.g.BAC-UP or FUSION-P from BASF Agricultural Specialities (Pty) Ltd., SouthAfrica), B. pumilus QST 2808 was isolated from soil collected inPohnpei, Federated States of Micronesia, in 1998 (NRRL B-30087; e.g.Sonata® or Ballad® Plus from Bayer Crop Science LP, USA), B. simplexABU288 (NRRL B-50304; U.S. Pat. No. 8,445,255), B. subtilis FB17 alsocalled UD 1022 or UD10-22 isolated from red beet roots in North America(ATCC PTA-11857; System. Appl. Microbiol. 27, 372-379, 2004; US2010/0260735; WO 2011/109395); B. thuringiensis ssp. aizawaiABTS-1857isolated from soil taken from a lawn in Ephraim, Wis., U.S.A., in 1987(also called ABG-6346; ATCC SD-1372; e.g. XenTari® from BioFa AG,Munsingen, Germany), B. t. ssp. kurstaki ABTS-351 identical to HD-1isolated in 1967 from diseased Pink Bollworm black larvae inBrownsville, Tex., U.S.A. (ATCC SD-1275; e.g. Dipel® DF from ValentBioSciences, IL, USA), B. t. ssp. kurstaki SB4 isolated from E.saccharina larval cadavers (NRRL B-50753; e.g. Beta Pro® from BASFAgricultural Specialities (Pty) Ltd., South Africa), B. t. ssp.tenebrionis NB-176-1, a mutant of strain NB-125, a wild type strainisolated in 1982 from a dead pupa of the beetle Tenebrio molitor (DSM5480; EP 585 215 B1; e.g. Novodor® from Valent BioSciences,Switzerland), Beauveria bassiana GHA (ATCC 74250; e.g. BotaniGard® 22WGPfrom Laverlam Int. Corp., USA), B. bassiana JW-1 (ATCC 74040; e.g.Naturalis® from CBC (Europe) S.r.l., Italy), B. bassiana PPRI 5339isolated from the larva of the tortoise beetle Conchyloctenia punctata(NRRL 50757; e.g. BroadBand® from BASF Agricultural Specialities (Pty)Ltd., South Africa), Bradyrhizobium elkanii strains SEMIA 5019 (alsocalled 29W) isolated in Rio de Janeiro, Brazil and SEMIA 587 isolated in1967 in the State of Rio Grande do Sul, from an area previouslyinoculated with a North American isolate, and used in commercialinoculants since 1968 (Appl. Environ. Microbiol. 73(8), 2635, 2007; e.g.GELFIX 5 from BASF Agricultural Specialties Ltd., Brazil), B. japonicum532c isolated from Wisconsin field in U.S.A. (Nitragin 61A152; Can. J.Plant. Sci. 70, 661-666, 1990; e.g. in Rhizoflo®, Histick®, Hicoat®Super from BASF Agricultural Specialties Ltd., Canada), B. japonicumE-109 variant of strain USDA 138 (INTA E109, SEMIA 5085; Eur. J. SoilBiol. 45, 28-35, 2009; Biol. Fertil. Soils 47, 81-89, 2011); B.japonicum strains deposited at SEMIA known from Appl. Environ.Microbiol. 73(8), 2635, 2007: SEMIA 5079 isolated from soil in Cerradosregion, Brazil by Embrapa-Cerrados used in commercial inoculants since1992 (CPAC 15; e.g. GELFIX 5 or ADHERE 60 from BASF AgriculturalSpecialties Ltd., Brazil), B. japonicum SEMIA 5080 obtained under labconditions by Embrapa-Cerrados in Brazil and used in commercialinoculants since 1992, being a natural variant of SEMIA 586 (CB1809)originally isolated in U.S.A. (CPAC 7; e.g. GELFIX 5 or ADHERE 60 fromBASF Agricultural Specialties Ltd., Brazil); Burkholderia sp. A396isolated from soil in Nikko, Japan, in 2008 (NRRL B-50319; WO2013/032693; Marrone Bio Innovations, Inc., USA), Coniothyrium minitansCON/M/91-08 isolated from oilseed rape (WO 1996/021358; DSM 9660; e.g.Contans® WG, Intercept® WG from Bayer CropScience AG, Germany), harpin(alpha-beta) protein (Science 257, 85-88, 1992; e.g. Messenger™ orHARP-N-Tek from Plant Health Care plc, U.K.), Helicoverpa armigeranucleopolyhedrovirus (HearNPV) (J. Invertebrate Pathol. 107, 112-126,2011; e.g. Helicovex® from Adermatt Biocontrol, Switzerland; Diplomata®from Koppert, Brazil; Vivus® Max from AgBiTech Pty Ltd., Queensland,Australia), Helicoverpa zea single capsid nucleopolyhedrovirus (HzSNPV)(e.g. Gemstar® from Certis LLC, USA), Helicoverpa zeanucleopolyhedrovirus ABA-NPV-U (e.g. Heligen® from AgBiTech Pty Ltd.,Queensland, Australia), Heterorhabditis bacteriophora (e.g. Nemasys® Gfrom BASF Agricultural Specialities Limited, UK), Isaria fumosoroseaApopka-97 isolated from mealy bug on gynura in Apopka, Fla., U.S.A.(ATCC 20874; Biocontrol Science Technol. 22(7), 747-761, 2012; e.g.PFR-97™ or PreFeRal® from Certis LLC, USA), Metarhizium anisopliae var.anisopliae F52 also called 275 or V275 isolated from codling moth inAustria (DSM 3884, ATCC 90448; e.g. Met52® Novozymes Biologicals BioAgGroup, Canada), Metschnikowia fructicola 277 isolated from grapes in thecentral part of Israel (U.S. Pat. No. 6,994,849; NRRL Y-30752; e.g.formerly Shemer® from Agrogreen, Israel), Paecilomyces ilacinus 251isolated from infected nematode eggs in the Philippines (AGAL 89/030550;WO1991/02051; Crop Protection 27, 352-361, 2008; e.g. BioAct® from BayerCropScience AG, Germany and MeloCon© from Certis, USA), PaeniBacillusa/vei NAS6G6 isolated from the rhizosphere of grasses in South Africa atleast before 2008 (WO 2014/029697; NRRL B-50755; e.g. BAC-UP from BASFAgricultural Specialities (Pty) Ltd., South Africa), PaeniBacillusstrains isolated from soil samples from a variety of European locationsincluding Germany: P. epiphyticus Lu17015 (WO 2016/020371; DSM 26971),P. polymyxa ssp. plantarum Lu16774 (WO 2016/020371; DSM 26969), P. p.ssp. plantarum strain Lu17007 (WO 2016/020371; DSM 26970); Pasteurianishizawae Pn1 isolated from a soybean field in the mid-2000s inIllinois, U.S.A. (ATCC SD-5833; Federal Register 76(22), 5808, Feb. 2,2011; e.g. Clariva™ PN from Syngenta Crop Protection, LLC, USA),Penicillium bilaiae (also called P. bilaii) strains ATCC 18309 (=ATCC74319), ATCC 20851 and/or ATCC 22348 (=ATCC 74318) originally isolatedfrom soil in Alberta, Canada (Fertilizer Res. 39, 97-103, 1994; Can. J.Plant Sci. 78(1), 91-102, 1998; U.S. Pat. No. 5,026,417, WO 1995/017806;e.g. Jump Start®, Provide® from Novozymes Biologicals BioAg Group,Canada), Reynoutria sachalinensis extract (EP 0307510 B1; e.g. Regalia©SC from Marrone BioInnovations, Davis, Calif., USA or Milsana® fromBioFa AG, Germany), Steinernema carpocapsae (e.g. Millenium® from BASFAgricultural Specialities Limited, UK), S. feltiae (e.g. Nemashield®from BioWorks, Inc., USA; Nemasys® from BASF Agricultural SpecialitiesLimited, UK), Streptomyces microflavus NRRL B-50550 (WO 2014/124369;Bayer CropScience, Germany), Trichoderma asperelloides JM41R isolated inSouth Africa (NRRL 50759; also referred to as T. fertile; e.g.Trichoplus® from BASF Agricultural Specialities (Pty) Ltd., SouthAfrica), T. harzianum T-22 also called KRL-AG2 (ATCC 20847; BioControl57, 687-696, 2012; e.g. Plantshield® from BioWorks Inc., USA or SabrEx™from Advanced Biological Marketing Inc., Van Wert, Ohio, USA).

According to one embodiment of the inventive mixtures, the at least onepesticide II is selected from the groups L1) to L6):

-   L1) Microbial pesticides with fungicidal, bactericidal, viricidal    and/or plant defense activator activity: Aureobasidium pullulans DSM    14940 and DSM 14941 (1.1), Bacillus amyloliquefaciens AP-188    (L.1.2), B. amyloliquefaciens ssp. plantarum D747 (L.1.3), B.    amyloliquefaciens ssp. plantarum FZB24 (L.1.4), B. amyloliquefaciens    ssp. plantarum FZB42 (L.1.5), B. amyloliquefaciens ssp. plantarum    MB1600 (L.1.6), B. amyloliquefaciens ssp. plantarum QST-713    (L.1.7), B. amyloliquefaciens ssp. plantarum TJ1000 (L.1.8), B.    pumilus GB34 (L.1.9), B. pumilus GHA 180 (L.1.10), B. pumilus INR-7    (L.1.11), B. pumilus QST 2808 (L.1.13), B. simplex ABU 288    (L.1.14), B. subtilis FB17 (L.1.15), Coniothyrium minitans    CON/M/91-08 (L.1.16), Metschnikowia fructicola NRRL Y-30752    (L.1.17), Penicillium bilaiae ATCC 22348 (L.1.19), P. bilaiae ATCC    20851 (L.1.20), Penicillium bilaiae ATCC 18309 (L.1.21),    Streptomyces microflavus NRRL B-50550 (L.1.22), T. harzianumT-22    (L.1.24);-   L2) Biochemical pesticides with fungicidal, bactericidal, viricidal    and/or plant defense activator activity: harpin protein (L.2.1),    Reynoutria sachalinensis extract (L.2.2);-   L3) Microbial pesticides with insecticidal, acaricidal, molluscidal    and/or nematicidal activity: Bacillus firmus 1-1582 (L.3.1); B.    thuringiensis ssp. aizawai ABTS-1857 (L.3.2), B. t. ssp. kurstaki    ABTS-351 (L.3.3), B. t. ssp. tenebrionis NB-176-1 (L.3.5), Beauveria    bassiana GHA (L.3.6), B. bassiana JW-1 (L.3.7), Burkholderia sp.    A396 (L.3.9), Helicoverpa armigera nucleopolyhedrovirus (HearNPV)    (L.3.10), Helicoverpa zea nucleopolyhedrovirus (HzNPV) ABA-NPV-U    (L.3.11), Helicoverpa zea single capsid nucleopolyhedrovirus    (HzSNPV) (L.3.12), Heterohabditis bacteriophora (L.3.13), Isaria    fumosorosea Apopka-97 (L.3.14), Metarhizium anisopliae var.    anisopliae F52 (L.3.15), Paecilomyces lilacinus 251 (L.3.16),    Pasteuria nishizawae Pn1 (L.3.17), Steinernema carpocapsae    (L.3.18), S. feltiae (L.3.19);-   L4) Biochemical pesticides with insecticidal, acaricidal,    molluscidal, pheromone and/or nematicidal activity: cis-jasmone    (L.4.1), methyl jasmonate (L.4.2), Quillay extract (L.4.3);-   L5) Microbial pesticides with plant stress reducing, plant growth    regulator, plant growth promoting and/or yield enhancing activity.

In a further aspect the present invention relates to an agrochemicalmixture comprising at least one fertilizer; and at least onenitrification inhibitor as defined as defined herein above; or at leastone fertilizer and a composition as mentioned above.

In the terms of the present invention “agrochemical mixture” means acombination of at least two compounds. The term is, however, notrestricted to a physical mixture comprising at least two compounds, butrefers to any preparation form of at least one compound and at least onefurther compound, the use of which many be time- and/or locus-related.

The agrochemical mixtures may, for example, be formulated separately butapplied in a temporal relationship, i.e. simultaneously or subsequently,the subsequent application having a time interval which allows acombined action of the compounds.

Furthermore, the individual compounds of the agrochemical mixturesaccording to the invention such as parts of a kit or parts of the binarymixture may be mixed by the user himself in a suitable mixing device. Inspecific embodiments further auxiliaries may be added, if appropriate.

The term “fertilizers” is to be understood as chemical compounds appliedto promote plant and fruit growth. Fertilizers are typically appliedeither through the soil (for uptake by plant roots), through soilsubstituents (also for uptake by plant roots), or by foliar feeding (foruptake through leaves). The term also includes mixtures of one or moredifferent types of fertilizers as mentioned below.

The term “fertilizers” can be subdivided into several categoriesincluding: a) organic fertilizers (composed of decayed plant/animalmatter), b) inorganic fertilizers (composed of chemicals and minerals)and c) urea-containing fertilizers.

Organic fertilizers include manure, e.g. liquid manure, semi-liquidmanure, biogas manure, stable manure or straw manure, slurry, wormcastings, peat, seaweed, compost, sewage, and guano. Green manure cropsare also regularly grown to add nutrients (especially nitrogen) to thesoil. Manufactured organic fertilizers include compost, blood meal, bonemeal and seaweed extracts. Further examples are enzyme digestedproteins, fish meal, and feather meal. The decomposing crop residue fromprior years is another source of fertility.

In addition, naturally occurring minerals such as mine rock phosphate,sulfate of potash and limestone are also considered inorganicfertilizers.

Inorganic fertilizers are usually manufactured through chemicalprocesses (such as the Haber process), also using naturally occurringdeposits, while chemically altering them (e.g. concentrated triplesuperphosphate). Naturally occurring inorganic fertilizers includeChilean sodium nitrate, mine rock phosphate, limestone, and raw potashfertilizers.

The inorganic fertilizer may, in a specific embodiment, be a NPKfertilizer. “NPK fertilizers” are inorganic fertilizers formulated inappropriate concentrations and combinations comprising the three mainnutrients nitrogen (N), phosphorus (P) and potassium (K) as well astypically S, Mg, Ca, and trace elements.

Urea-containing fertilizer may, in specific embodiments, be urea,formaldehyde urea, anhydrous ammonium, urea ammonium nitrate (UAN)solution, urea sulfur, urea based NPK-fertilizers, or urea ammoniumsulfate. Also envisaged is the use of urea as fertilizer. In caseurea-containing fertilizers or urea are used or provided, it isparticularly preferred that urease inhibitors as defined herein abovemay be added or additionally be present, or be used at the same time orin connection with the urea-containing fertilizers.

Fertilizers may be provided in any suitable form, e.g. as solid coatedor uncoated granules, in liquid or semi-liquid form, as sprayablefertilizer, or via fertigation etc.

Coated fertilizers may be provided with a wide range of materials.Coatings may, for example, be applied to granular or prilled nitrogen(N) fertilizer or to multi-nutrient fertilizers. Typically, urea is usedas base material for most coated fertilizers. Alternatively, ammonium orNPK fertilizers are used as base material for coated fertilizers. Thepresent invention, however, also envisages the use of other basematerials for coated fertilizers, any one of the fertilizer materialsdefined herein. In certain embodiments, elemental sulfur may be used asfertilizer coating. The coating may be performed by spraying molten Sover urea granules, followed by an application of sealant wax to closefissures in the coating. In a further embodiment, the S layer may becovered with a layer of organic polymers, preferably a thin layer oforganic polymers.

Further envisaged coated fertilizers may be provided by reactingresin-based polymers on the surface of the fertilizer granule. A furtherexample of providing coated fertilizers includes the use of lowpermeability polyethylene polymers in combination with high permeabilitycoatings.

In specific embodiments the composition and/or thickness of thefertilizer coating may be adjusted to control, for example, the nutrientrelease rate for specific applications. The duration of nutrient releasefrom specific fertilizers may vary, e.g. from several weeks to manymonths. The presence of nitrification inhibitors in a mixture withcoated fertilizers may accordingly be adapted. It is, in particular,envisaged that the nutrient release involves or is accompanied by therelease of an nitrification inhibitor according to the presentinvention.

Coated fertilizers may be provided as controlled release fertilizers(CRFs). In specific embodiments these controlled release fertilizers arefully coated urea or N—P—K fertilizers, which are homogeneous and whichtypically show a pre-defined longevity of release. In furtherembodiments, the CRFs may be provided as blended controlled releasefertilizer products which may contain coated, uncoated and/or slowrelease components. In certain embodiments, these coated fertilizers mayadditionally comprise micronutrients. In specific embodiments thesefertilizers may show a pre-defined longevity, e.g. in case of N—P—Kfertilizers.

Additionally envisaged examples of CRFs include patterned releasefertilizers. These fertilizers typically show a pre-defined releasepatterns (e.g. hi/standard/lo) and a pre-defined longevity. In exemplaryembodiments fully coated N—P—K, Mg and micronutrients may be deliveredin a patterned release manner.

Also envisaged are double coating approaches or coated fertilizers basedon a programmed release.

In further embodiments the fertilizer mixture may be provided as, or maycomprise or contain a slow release fertilizer. The fertilizer may, forexample, be released over any suitable period of time, e.g. over aperiod of 1 to 5 months, preferably up to 3 months.

Typical examples of ingredients of slow release fertilizers are IBDU(isobutylidenediurea), e.g. containing about 31-32% nitrogen, of which90% is water insoluble; or UF, i.e. an urea-formaldehyde product whichcontains about 38% nitrogen of which about 70% may be provided as waterinsoluble nitrogen; or CDU (crotonylidene diurea) containing about 32%nitrogen; or MU (methylene urea) containing about 38 to 40% nitrogen, ofwhich 25-60% is typically cold water insoluble nitrogen; or MDU(methylene diurea) containing about 40% nitrogen, of which less than 25%is cold water insoluble nitrogen; or MO (methylol urea) containing about30% nitrogen, which may typically be used in solutions; or DMTU(diimethylene triurea) containing about 40% nitrogen, of which less than25% is cold water insoluble nitrogen; or TMTU (tri methylene tetraurea),which may be provided as component of UF products; or TMPU (trimethylene pentaurea), which may also be provided as component of UFproducts; or UT (urea triazone solution) which typically contains about28% nitrogen. The fertilizer mixture may also be long-termnitrogen-bearing fertiliser containing a mixture of acetylene diurea andat least one other organic nitrogen-bearing fertiliser selected frommethylene urea, isobutylidene diurea, crotonylidene diurea, substitutedtriazones, triuret or mixtures thereof.

Any of the above mentioned fertilizers or fertilizer forms may suitablybe combined. For instance, slow release fertilizers may be provided ascoated fertilizers. They may also be combined with other fertilizers orfertilizer types. The same applies to the presence of a nitrificationinhibitor according to the present invention, which may be adapted tothe form and chemical nature of the fertilizer and accordingly beprovided such that its release accompanies the release of thefertilizer, e.g. is released at the same time or with the samefrequency. The present invention further envisages fertilizer orfertilizer forms as defined herein above in combination withnitrification inhibitors as defined herein above and further incombination with urease inhibitors as defined herein above. Suchcombinations may be provided as coated or uncoated forms and/or as slowor fast release forms. Preferred are combinations with slow releasefertilizers including a coating. In further embodiments, also differentrelease schemes are envisaged, e.g. a slower or a faster release.

The term “fertigation” as used herein refers to the application offertilizers, optionally soil amendments, and optionally otherwater-soluble products together with water through an irrigation systemto a plant or to the locus where a plant is growing or is intended togrow, or to a soil substituent as defined herein below. For example,liquid fertilizers or dissolved fertilizers may be provided viafertigation directly to a plant or a locus where a plant is growing oris intended to grow. Likewise, nitrification inhibitors according to thepresent invention, or in combination with additional nitrificationinhibitors, may be provided via fertigation to plants or to a locuswhere a plant is growing or is intended to grow. Fertilizers andnitrification inhibitors according to the present invention, or incombination with additional nitrification inhibitors, may be providedtogether, e.g. dissolved in the same charge or load of material(typically water) to be irrigated. In further embodiments, fertilizersand nitrification inhibitors may be provided at different points intime. For example, the fertilizer may be fertigated first, followed bythe nitrification inhibitor, or preferably, the nitrification inhibitormay be fertigated first, followed by the fertilizer. The time intervalsfor these activities follow the herein above outlined time intervals forthe application of fertilizers and nitrification inhibitors. Alsoenvisaged is a repeated fertigation of fertilizers and nitrificationinhibitors according to the present invention, either together orintermittently, e.g. every 2 hours, 6 hours, 12 hours, 24 hours, 2 days,3 days, 4 days, 5 days, 6 days or more.

In particularly preferred embodiments, the fertilizer is anammonium-containing fertilizer.

The agrochemical mixture according to the present invention may compriseone fertilizer as defined herein above and one nitrification inhibitorof formula I as defined herein above. In further embodiments, theagrochemical mixture according to the present invention may comprise atleast one or more than one fertilizer as defined herein above, e.g. 2,3, 4, 5, 6, 6, 7, 8, 9, 10 or more different fertilizers (includinginorganic, organic and urea-containing fertilizers) and at least onenitrification inhibitor of formula I as defined herein above, preferablyone nitrification inhibitor of formula I selected from Table 1.

In another group of embodiments the agrochemical mixture according tothe present invention may comprise at least one or more than onenitrification inhibitor of formula I as defined herein above, preferablymore than one nitrification inhibitor of formula I selected from Table1, e.g. 2, 3, 4, 5, 6, 6, 7, 8, 9, 10 or more different nitrificationinhibitors as defined herein above or as provided in Table 1 and atleast one fertilizer as defined herein above.

The term “at least one” is to be understood as 1, 2, 3 or more of therespective compound selected from the group consisting of fertilizers asdefined herein above (also designated as compound A), and nitrificationinhibitors of formula I as defined herein above (also designated ascompound B).

In addition to at least one fertilizer and at least one nitrificationinhibitor as defined herein above, an agrochemical mixture may comprisefurther ingredients, compounds, active compounds or compositions or thelike. For example, the agrochemical mixture may additionally comprise orcomposed with or on the basis of a carrier, e.g. an agrochemicalcarrier, preferably as defined herein. In further embodiments, theagrochemical mixture may further comprise at least one pesticidalcompound. For example, the agrochemical mixture may additionallycomprise at least one herbicidal compound and/or at least one fungicidalcompound and/or at least one insecticidal compound.

In further embodiments, the agrochemical mixture may, in addition to theabove indicated ingredients, in particular in addition to thenitrification inhibitor of the compound of formula I and the fertilizer,further comprise alternative or additional nitrification inhibitors suchas linoleic acid, alpha-linolenic acid, methyl p-coumarate, methylferulate, MHPP, Karanjin, brachialacton, p-benzoquinone sorgoleone,nitrapyrin, dicyandiamide (DCD), 3,4-dimethyl pyrazole phosphate (DMPP),4-amino-1,2,4-triazole hydrochloride (ATC), 1-amido-2-thiourea (ASU),2-amino-4-chloro-6-methylpyrimidine (AM),5-ethoxy-3-trichloromethyl-1,2,4-thiodiazole (terrazole),ammoniumthiosulfate (ATU), 3-methylpyrazol (3-MP), 3,5-dimethylpyrazole(DMP), 1,2,4-triazol and thiourea (TU) and/or sulfathiazole (ST),N-(1H-pyrazolyl-methyl)acetamides such asN-((3(5)-methyl-1H-pyrazole-1-yl)methyl)acetamide, and/orN-(1H-pyrazolyl-methyl)formamides such asN-((3(5)-methyl-1H-pyrazole-1-yl)methyl formamide,N-(4-chloro-3(5)-methyl-pyrazole-1-ylmethyl)-formamide, orN-(3(5),4-dimethyl-pyrazole-1-ylmethyl)-formamide.

Furthermore, the invention relates to a method for reducingnitrification, comprising treating a plant growing on soil and/or thelocus where the plant is growing or is intended to grow with at leastone nitrification inhibitor as defined herein above, i.e. with annitrification inhibitor being a compound of formula I, or a derivativethereof, or a composition comprising said nitrification inhibitor.

The term “plant” is to be understood as a plant of economic importanceand/or men-grown plant. In certain embodiments, the term may also beunderstood as plants which have no or no significant economicimportance. The plant is preferably selected from agricultural,silvicultural and horticultural (including ornamental) plants. The termalso relates to genetically modified plants.

The term “plant” as used herein further includes all parts of a plantsuch as germinating seeds, emerging seedlings, plant propagules,herbaceous vegetation as well as established woody plants including allbelowground portions (such as the roots) and aboveground portions.

Within the context of the method for reducing nitrification it isassumed that the plant is growing on soil. In specific embodiments, theplant may also grow differently, e.g. in synthetic laboratoryenvironments or on soil substituents, or be supplemented with nutrients,water etc. by artificial or technical means. In such scenarios, theinvention envisages a treatment of the zone or area where the nutrients,water etc. are provided to the plant. Also envisaged is that the plantgrows in green houses or similar indoor facilities.

The term “locus” is to be understood as any type of environment, soil,soil substituent, area or material where the plant is growing orintended to grow. Preferably, the term relates to soil or soilsubstituent on which a plant is growing.

In one embodiment, the plant to be treated according to the method ofthe invention is an agricultural plant. “Agricultural plants” are plantsof which a part (e.g. seeds) or all is harvested or cultivated on acommercial scale or which serve as an important source of feed, food,fibers (e.g. cotton, linen), combustibles (e.g. wood, bioethanol,biodiesel, biomass) or other chemical compounds. Preferred agriculturalplants are for example cereals, e.g. wheat, rye, barley, triticale,oats, corn, sorghum or rice, beet, e.g. sugar beet or fodder beet;fruits, such as pomes, stone fruits or soft fruits, e.g. apples, pears,plums, peaches, almonds, cherries, strawberries, raspberries,blackberries or gooseberries; leguminous plants, such as lentils, peas,alfalfa or soybeans; oil plants, such as rape, oilseed rape, canola,linseed, mustard, olives, sunflowers, coconut, cocoa beans, castor oilplants, oil palms, ground nuts or soybeans; cucurbits, such as squashes,cucumber or melons; fiber plants, such as cotton, flax, hemp or jute;citrus fruit, such as oranges, lemons, grapefruits or mandarins;vegetables, such as spinach, lettuce, asparagus, cabbages, carrots,onions, tomatoes, potatoes, cucurbits or paprika; lauraceous plants,such as avocados, cinnamon or camphor; energy and raw material plants,such as corn, soybean, rape, canola, sugar cane or oil palm; tobacco;nuts; coffee; tea; bananas; vines (table grapes and grape juice grapevines); hop; turf; natural rubber plants.

In a further embodiment, the plant to be treated according to the methodof the invention is a horticultural plant. The term “horticulturalplants” are to be understood as plants which are commonly used inhorticulture, e.g. the cultivation of ornamentals, vegetables and/orfruits. Examples for ornamentals are turf, geranium, pelargonia,petunia, begonia and fuchsia. Examples for vegetables are potatoes,tomatoes, peppers, cucurbits, cucumbers, melons, watermelons, garlic,onions, carrots, cabbage, beans, peas and lettuce and more preferablyfrom tomatoes, onions, peas and lettuce. Examples for fruits are apples,pears, cherries, strawberry, citrus, peaches, apricots and blueberries.

In a further embodiment, the plant to be treated according to the methodof the invention is an ornamental plant. “Ornamental plants” are plantswhich are commonly used in gardening, e.g. in parks, gardens and onbalconies. Examples are turf, geranium, pelargonia, petunia, begonia andfuchsia.

In another embodiment of the present invention, the plant to be treatedaccording to the method of the invention is a silvicultural plant. Theterm “silvicultural plant” is to be understood as trees, morespecifically trees used in reforestation or industrial plantations.Industrial plantations generally serve for the commercial production offorest products, such as wood, pulp, paper, rubber tree, Christmastrees, or young trees for gardening purposes. Examples for silviculturalplants are conifers, like pines, in particular Pinus spec., fir andspruce, eucalyptus, tropical trees like teak, rubber tree, oil palm,willow (Salix), in particular Salix spec., poplar (cottonwood), inparticular Populus spec., beech, in particular Fagus spec., birch, oilpalm, and oak.

The term “plant propagation material” is to be understood to denote allthe generative parts of the plant such as seeds and vegetative plantmaterial such as cuttings and tubers (e.g. potatoes), which can be usedfor the multiplication of the plant. This includes seeds, grains, roots,fruits, tubers, bulbs, rhizomes, cuttings, spores, offshoots, shoots,sprouts and other parts of plants, including seedlings and young plants,which are to be transplanted after germination or after emergence fromsoil, meristem tissues, single and multiple plant cells and any otherplant tissue from which a complete plant can be obtained.

The term “genetically modified plants” is to be understood as plants,which genetic material has been modified by the use of recombinant DNAtechniques in a way that under natural circumstances it cannot readilybe obtained by cross breeding, mutations or natural recombination.Typically, one or more genes have been integrated into the geneticmaterial of a genetically modified plant in order to improve certainproperties of the plant. Such genetic modifications also include but arenot limited to targeted post-translational modification of protein(s),oligo- or polypeptides e.g. by glycosylation or polymer additions suchas prenylated, acetylated or farnesylated moieties or PEG moieties.

Plants that have been modified by breeding, mutagenesis or geneticengineering, e.g. have been rendered tolerant to applications ofspecific classes of herbicides, such as auxin herbicides such as dicambaor 2,4-D; bleacher herbicides such as hydroxylphenylpyruvate dioxygenase(HPPD) inhibitors or phytoene desaturase (PDS) inhibitors; acetolactatesynthase (ALS) inhibitors such as sulfonyl ureas or imidazolinones;enolpyruvylshikimate-3-phosphate synthase (EPSPS) inhibitors, such asglyphosate; glutamine synthetase (GS) inhibitors such as glufosinate;protoporphyrinogen-IX oxidase inhibitors; lipid biosynthesis inhibitorssuch as acetyl CoA carboxylase (ACCase) inhibitors; or oxynil (i.e.bromoxynil or ioxynil) herbicides as a result of conventional methods ofbreeding or genetic engineering.

Furthermore, plants have been made resistant to multiple classes ofherbicides through multiple genetic modifications, such as resistance toboth glyphosate and glufosinate or to both glyphosate and a herbicidefrom another class such as ALS inhibitors, HPPD inhibitors, auxinherbicides, or ACCase inhibitors. These herbicide resistancetechnologies are e.g. described in Pest Managem. Sci. 61, 2005, 246; 61,2005, 258; 61, 2005, 277; 61, 2005, 269; 61, 2005, 286; 64, 2008, 326;64, 2008, 332; Weed Sci. 57, 2009, 108; Austral. J. Agricult. Res. 58,2007, 708; Science 316, 2007, 1185; and references quoted therein.Several cultivated plants have been rendered tolerant to herbicides byconventional methods of breeding (mutagenesis), e.g. Clearfield® summerrape (Canola, BASF SE, Germany) being tolerant to imidazolinones, e.g.imazamox, or ExpressSun® sunflowers (DuPont, USA) being tolerant tosulfonyl ureas, e.g. tribenuron. Genetic engineering methods have beenused to render cultivated plants such as soybean, cotton, corn, beetsand rape, tolerant to herbicides such as glyphosate and glufosinate,some of which are commercially available under the trade namesRoundupReady® (glyphosate-tolerant, Monsanto, U.S.A.), Cultivance®(imidazolinone tolerant, BASF SE, Germany) and LibertyLink®(glufosinate-tolerant, Bayer CropScience, Germany).

Furthermore, plants are also covered that are by the use of recombinantDNA techniques capable to synthesize one or more insecticidal proteins,especially those known from the bacterial genus Bacillus, particularlyfrom Bacillus thuringiensis, such as δ-endotoxins, e.g. CryIA(b),CryIA(c), CryIF, CryIF(a2), CryIIA(b), CryIIIA, CryIIIB(b1) or Cry9c;vegetative insecticidal proteins (VIP), e.g. VIP1, VIP2, VIP3 or VIP3A;insecticidal proteins of bacteria colonizing nematodes, e.g.Photorhabdus spp. or Xenorhabdus spp.; toxins produced by animals, suchas scorpion toxins, arachnid toxins, wasp toxins, or otherinsect-specific neurotoxins; toxins produced by fungi, suchStreptomycetes toxins, plant lectins, such as pea or barley lectins;agglutinins; proteinase inhibitors, such as trypsin inhibitors, serineprotease inhibitors, patatin, cystatin or papain inhibitors;ribosome-inactivating proteins (RIP), such as ricin, maize-RIP, abrin,luffin, saporin or bryodin; steroid metabolism enzymes, such as3-hydroxysteroid oxidase, ecdysteroid-IDP-glycosyl-transferase,cholesterol oxidases, ecdysone inhibitors or HMG-CoA-reductase; ionchannel blockers, such as blockers of sodium or calcium channels;juvenile hormone esterase; diuretic hormone receptors (helicokininreceptors); stilbene synthase, bibenzyl synthase, chitinases orglucanases. In the context of the present invention these insecticidalproteins or toxins are to be understood expressly also as pre-toxins,hybrid proteins, truncated or otherwise modified proteins. Hybridproteins are characterized by a new combination of protein domains,(see, e.g. WO 02/015701). Further examples of such toxins or geneticallymodified plants capable of synthesizing such toxins are disclosed, e.g.,in EP-A 374 753, WO 93/007278, WO 95/34656, EP-A 427 529, EP-A 451 878,WO 03/18810 und WO 03/52073.

The methods for producing such genetically modified plants are generallyknown to the person skilled in the art and are described, e.g. in thepublications mentioned above. These insecticidal proteins contained inthe genetically modified plants impart to the plants producing theseproteins tolerance to harmful pests from all taxonomic groups ofarthropods, especially to beetles (Coleoptera), two-winged insects(Diptera), and moths (Lepidoptera) and to nematodes (Nematoda).Genetically modified plants capable to synthesize one or moreinsecticidal proteins are, e.g., described in the publications mentionedabove, and some of which are commercially available such as YieldGard®(corn cultivars producing the Cry1Ab toxin), YieldGard® Plus (corncultivars producing Cry1Ab and Cry3Bb1 toxins), Starlink® (corncultivars producing the Cry9c toxin), Herculex® RW (corn cultivarsproducing Cry34Ab1, Cry35Ab1 and the enzymephosphinothricin-N-acetyltransferase [PAT]); NuCOTN® 33B (cottoncultivars producing the Cry1Ac toxin), Bollgard® I (cotton cultivarsproducing the Cry1Ac toxin), Bollgard® II (cotton cultivars producingCry1Ac and Cry2Ab2 toxins); VIPCOT® (cotton cultivars producing aVIP-toxin); NewLeaf® (potato cultivars producing the Cry3A toxin);Bt-Xtra®, NatureGard®, KnockOut®, BiteGard®, Protecta®, Bt11 (e.g.Agrisure® CB) and Bt176 from Syngenta Seeds SAS, France, (corn cultivarsproducing the Cry1Ab toxin and PAT enzyme), MIR604 from Syngenta SeedsSAS, France (corn cultivars producing a modified version of the Cry3Atoxin, c.f. WO 03/018810), MON 863 from Monsanto Europe S.A., Belgium(corn cultivars producing the Cry3Bb1 toxin), IPC 531 from MonsantoEurope S.A., Belgium (cotton cultivars producing a modified version ofthe Cry1Ac toxin) and 1507 from Pioneer Overseas Corporation, Belgium(corn cultivars producing the Cry1F toxin and PAT enzyme).

Furthermore, plants are also covered that are by the use of recombinantDNA techniques capable to synthesize one or more proteins to increasethe resistance or tolerance of those plants to bacterial, viral orfungal pathogens. Examples of such proteins are the so-called“pathogenesis-related proteins” (PR proteins, see, e.g. EP-A 392 225),plant disease resistance genes (e.g. potato cultivars, which expressresistance genes acting against Phytophthora infestans derived from theMexican wild potato Solanum bulbocastanum) or T4-lysozym (e.g. potatocultivars capable of synthesizing these proteins with increasedresistance against bacteria such as Erwinia amylvora). The methods forproducing such genetically modified plants are generally known to theperson skilled in the art and are described, e.g. in the publicationsmentioned above.

Furthermore, plants are also covered that are by the use of recombinantDNA techniques capable to synthesize one or more proteins to increasethe productivity (e.g. bio mass production, grain yield, starch content,oil content or protein content), tolerance to drought, salinity or othergrowth-limiting environmental factors or tolerance to pests and fungal,bacterial or viral pathogens of those plants.

Furthermore, plants are also covered that contain by the use ofrecombinant DNA techniques a modified amount of substances of content ornew substances of content, specifically to improve human or animalnutrition, e.g. oil crops that produce health-promoting long-chainomega-3 fatty acids or unsaturated omega-9 fatty acids (e.g. Nexera®rape, DOW Agro Sciences, Canada).

Furthermore, plants are also covered that contain by the use ofrecombinant DNA techniques a modified amount of substances of content ornew substances of content, specifically to improve raw materialproduction, e.g. potatoes that produce increased amounts of amylopectin(e.g. Amflora® potato, BASF SE, Germany).

The term “soil substituent” as used herein refers to a substrate whichis able to allow the growth of a plant and does not comprise usual soilingredients. This substrate is typically an inorganic substrate whichmay have the function of an inert medium. It may, in certainembodiments, also comprise organic elements or portions. Soilsubstituents may, for example, be used in hydroculture or hydroponicapproaches, i.e. wherein plants are grown in soilless medium and/oraquatic based environments. Examples of suitable soil substituents,which may be used in the context of the present invention, are perlite,gravel, biochar, mineral wool, coconut husk, phyllosilicates, i.e. sheetsilicate minerals, typically formed by parallel sheets of silicatetetrahedra with Si₂O₅ or a 2:5 ratio, or clay aggregates, in particularexpanded clay aggregates with a diameter of about 10 to 40 mm.Particularly preferred is the employment of vermiculite, i.e. aphyllosilicate with 2 tetrahedral sheets for every one octahedral sheetpresent.

The use of soil substituents may, in specific embodiments, be combinedwith fertigation or irrigation as defined herein.

In specific embodiments, the treatment may be carried out during allsuitable growth stages of a plant as defined herein. For example, thetreatment may be carried out during the BBCH principle growth stages.

The term “BBCH principal growth stage” refers to the extended BBCH-scalewhich is a system for a uniform coding of phenologically similar growthstages of all mono- and dicotyledonous plant species in which the entiredevelopmental cycle of the plants is subdivided into clearlyrecognizable and distinguishable longer-lasting developmental phases.The BBCH-scale uses a decimal code system, which is divided intoprincipal and secondary growth stages. The abbreviation BBCH derivesfrom the Federal Biological Research Centre for Agriculture and Forestry(Germany), the Bundessortenamt (Germany) and the chemical industry.

In one embodiment the invention relates to a method for reducingnitrification comprising treating a plant growing on soil or soilsubstituents and/or the locus where the plant is growing or is intendedto grow with at least one nitrification inhibitor as defined hereinabove, i.e. with a nitrification inhibitor being a compound of formulaI, or a derivative thereof at a growth stage (GS) between GS 00 andGS>BBCH 99 of the pant (e.g. when fertilizing in fall after harvestingapples) and preferably between GS 00 and GS 65 BBCH of the plant.

In one embodiment the invention relates to a method for reducingnitrification comprising treating a plant growing on soil or soilsubstituents and/or the locus where the plant is growing or is intendedto grow with at least one nitrification inhibitor as defined hereinabove, i.e. with a nitrification inhibitor being a compound of formulaI, or a derivative thereof at a growth stage (GS) between GS 00 to GS45, preferably between GS 00 and GS 40 BBCH of the plant.

In a preferred embodiment the invention relates to a method for reducingnitrification comprising treating a plant growing on soil or soilsubstituents and/or the locus where the plant is growing or is intendedto grow with at least one nitrification inhibitor as defined hereinabove, i.e. with a nitrification inhibitor being a compound of formulaI, or a derivative thereof at an early growth stage (GS), in particulara GS 00 to GS 05, or GS 00 to GS 10, or GS 00 to GS 15, or GS 00 to GS20, or GS 00 to GS 25 or GS 00 to GS 33 BBCH of the plant.

In particularly preferred embodiments, the method for reducingnitrification comprises treating a plant growing on soil or soilsubstituents and/or the locus where the plant is growing or is intendedto grow with at least one nitrification inhibitor as defined hereinabove during growth stages including GS 00.

In a further, specific embodiment of the invention, at least onenitrification inhibitor as defined herein above, i.e. a nitrificationinhibitor being a compound of formula I, or a derivative thereof isapplied to a plant growing on soil or soil substituents and/or the locuswhere the plant is growing or is intended to grow at a growth stagebetween GS 00 and GS 55 BBCH, or of the plant.

In a further embodiment of the invention, at least one nitrificationinhibitor as defined herein above, i.e. a nitrification inhibitor beinga compound of formula I, or a derivative thereof is applied to a plantgrowing on soil or soil substituents and/or the locus where the plant isgrowing or is intended to grow at the growth stage between GS 00 and GS47 BBCH of the plant.

In one embodiment of the invention, at least one nitrification inhibitoras defined herein above, i.e. a nitrification inhibitor being a compoundof formula I, or a derivative thereof is applied to a plant growing onsoil or soil substituents and/or the locus where the plant is growing oris intended to grow before and at sowing, before emergence, and untilharvest (GS 00 to GS 89 BBCH), or at a growth stage (GS) between GS 00and GS 65 BBCH of the plant.

In a preferred embodiment the invention relates to a method for reducingnitrification comprising treating a plant growing on soil or soilsubstituents and/or the locus where the plant is growing with at leastone nitrification inhibitor as defined herein above, i.e. with anitrification inhibitor being a compound of formula I, or a derivativethereof wherein the plant and/or the locus where plant is growing or isintended to grow is additionally provided with at least one fertilizer.The fertilizer may be any suitable fertilizer, preferably a fertilizeras defined herein above. Also envisaged is the application of more thanone fertilizer, e.g. 2, 3, 4, 5, 6, 7, 8, 9, 10 fertilizers, or ofdifferent fertilizer classes or categories.

In specific embodiments of the invention, at least one nitrificationinhibitor as defined herein above, i.e. a nitrification inhibitor beinga compound of formula I, or a derivative thereof and at least onefertilizer is applied to a plant growing on soil or soil substituentsand/or the locus where the plant is growing or is intended to grow at agrowth stage between GS 00 and GS 33 BBCH of the plant.

In specific embodiments of the invention, at least one nitrificationinhibitor as defined herein above, i.e. a nitrification inhibitor beinga compound of formula I, or a derivative thereof and at least onefertilizer is applied to a plant growing on soil or soil substituentsand/or the locus where the plant is growing or is intended to grow at agrowth stage between GS 00 and GS 55 BBCH of the plant.

In further specific embodiments of the invention, at least onenitrification inhibitor as defined herein above, i.e. a nitrificationinhibitor being a compound of formula I, or a derivative thereof and atleast one fertilizer is applied to a plant growing on soil or soilsubstituents and/or the locus where the plant is growing or is intendedto grow at sowing, before emergence, or at a growth stage (GS) betweenGS 00 and GS>BBCH 99 of the pant (e.g. when fertilizing in fall afterharvesting apples) and preferably between GS 00 and 65 BBCH of theplant.

According to a preferred embodiment of the present invention theapplication of said nitrification inhibitor and of said fertilizer asdefined herein above is carried out simultaneously or with a time lag.The term “time lag” as used herein means that either the nitrificationinhibitor is applied before the fertilizer to the plant growing on soilor soil substituents and/or the locus where the plant is growing or isintended to grow; or the fertilizer is applied before the nitrificationinhibitor to the plant growing on soil or soil substituents and/or thelocus where the plant is growing or is intended to grow. Such time lagmay be any suitable period of time which still allows to provide anitrification inhibiting effect in the context of fertilizer usage. Forexample, the time lag may be a time period of 1 day, 2 days, 3 days, 4days, 5 days, 6 days, 7 days, 8 days, 9 days, 10 days, 11 days, 12 days,13 days, 14 days, 3 weeks 4 weeks, 5 weeks, 6 weeks, 7 weeks, 8 weeks, 9weeks, 10 weeks, 11 weeks, 12 weeks, 4 months, 5 months, 6 months, 7months, 8 months, 9 months, 10 months or more or any time period inbetween the mentioned time periods. Preferably, the time lag is aninterval of 1 day, 2 days, 3 days, 1 week, 2 weeks or 3 weeks. The timelag preferably refers to situations in which the nitrification inhibitoras defined above is provided 1 day, 2 days, 3 days, 4 days, 5 days, 6days, 7 days, 8 days, 9 days, 10 days, 11 days, 12 days, 13 days, 14days, 3 weeks 4 weeks, 5 weeks, 6 weeks, 7 weeks, 8 weeks, 9 weeks, 10weeks, 11 weeks, 12 weeks, 4 months, 5 months, 6 months, 7 months, 8months, 9 months, 10 months or more or any time period in between thementioned time periods before the application of a fertilizer as definedherein above.

In another specific embodiment of the invention at least onenitrification inhibitor as defined herein above, i.e. a nitrificationinhibitor being a compound of formula I, or a derivative thereof isapplied between GS 00 to GS 33 BBCH of the plant, or between GS 00 andGS 65 BBCH of the plant, provided that the application of at least onefertilizer as defined herein above is carried out with a time lag of atleast 1 day, e.g. a time lag of 1 day, 2 days, 3 days, 4 days, 5 days, 6days, 7 days, 8 days, 9 days, 10 days, 11 days, 12 days, 13 days, 14days, 3 weeks 4 weeks, 5 weeks, 6 weeks, 7 weeks, 8 weeks, 9 weeks, 10weeks, or more or any time period in between the mentioned time periods.It is preferred that the nitrification inhibitors, which is appliedbetween GS 00 to GS 33 BBCH of the plant, is provided 1 day, 2 days, 3days, 4 days, 5 days, 6 days, 7 days, 8 days, 9 days, 10 days, 11 days,12 days, 13 days, 14 days, 3 weeks 4 weeks, 5 weeks, 6 weeks, 7 weeks, 8weeks, 9 weeks, 10 weeks, 11 weeks, or 12 weeks before the applicationof a fertilizer as defined herein above.

In another specific embodiment of the invention, at least one fertilizeras defined herein above is applied between GS 00 to GS 33 BBCH of theplant or between GS 00 and GS 65 BBCH of the plant, provided that theapplication of at least one nitrification inhibitor as defined hereinabove, i.e. of a nitrification inhibitor being a compound of formula I,or a derivative thereof, is carried out with a time lag of at least 1day, e.g. a time lag of 1 day, 2 days, 3 days, 4 days, 5 days, 6 days, 7days, 8 days, 9 days, 10 days, 11 days, 12 days, 13 days, 14 days, 3weeks 4 weeks, 5 weeks, 6 weeks, 7 weeks, 8 weeks, 9 weeks, 10 weeks ormore or any time period in between the mentioned time periods.

According to a specific embodiment of the present invention a plantgrowing on soil or soil substituents and/or the locus where the plant isgrowing or is intended to grow is treated at least once with anitrification inhibitor as defined herein above, i.e. with anitrification inhibitor being a compound of formula I, or a derivativethereof. In a further specific embodiment of the present invention aplant growing on soil or soil substituents and/or the locus where theplant is growing or is intended to grow is treated at least once with anitrification inhibitor as defined herein above, i.e. with anitrification inhibitor being a compound of formula I, or a derivativethereof, and at least once with a fertilizer as defined herein above.

The term “at least once” means that the application may be performed onetime, or several times, i.e. that a repetition of the treatment with anitrification inhibitor and/or a fertilizer may be envisaged. Such arepetition may a 2 times, 3 times, 4 times, 5 times, 6 times, 7 times, 8times, 9 times, 10 times or more frequent repetition of the treatmentwith a nitrification inhibitor and/or a fertilizer. The repetition oftreatment with a nitrification inhibitor and a fertilizer may further bedifferent. For example, while the fertilizer may be applied only once,the nitrification inhibitor may be applied 2 times, 3 times, 4 timesetc.

Alternatively, while the nitrification inhibitor may be applied onlyonce, the fertilizer may be applied 2 times, 3 times, 4 times etc.Further envisaged are all combination of numerical different numbers ofrepetitions for the application of a nitrification inhibitor and afertilizer as defined herein above.

Such a repeated treatment may further be combined with a time lagbetween the treatment of the nitrification inhibitor and the fertilizeras described above.

The time interval between a first application and second or subsequentapplication of a nitrification inhibitor and/or a fertilizer may be anysuitable interval. This interval may range from a few seconds up to 3months, e.g. from a few seconds up to 1 month, or from a few seconds upto 2 weeks. In further embodiments, the time interval may range from afew seconds up to 3 days or from 1 second up to 24 hours.

In further specific embodiments, a method for reducing nitrification asdescribed above is carried out by treating a plant growing on soil orsoil substituents and/or the locus where the plant is growing or isintended to grow with at least one agrochemical mixture as definedherein above, or with a composition for reducing nitrification asdefined herein above.

In another embodiment of the invention, an agrochemical mixturecomprising an ammonium- or urea-containing fertilizer and at least onenitrification inhibitor as defined herein above is applied before and atsowing, before emergence, and until GS>BBCH 99 of the pant (e.g. whenfertilizing in fall after harvesting apples In case the agrochemicalmixture is provided as kit of parts or as non-physical mixture, it maybe applied with a time lag between the application of the nitrificationinhibitor and the fertilizer or between the application of thenitrification inhibitor a secondary or further ingredient, e.g. apesticidal compound as mentioned herein above.

In a further embodiment plant propagules are preferably treatedsimultaneously (together or separately) or subsequently.

The term “propagules” or “plant propagules” is to be understood todenote any structure with the capacity to give rise to a new plant, e.g.a seed, a spore, or a part of the vegetative body capable of independentgrowth if detached from the parent. In a preferred embodiment, the term“propagules” or “plant propagules” denotes for seed.

For a method as described above, or for a use according to theinvention, in particular for seed treatment and in furrow application,the application rates of nitrification inhibitors, i.e. of the compoundof formula I are between 0.01 g and 5 kg of active ingredient perhectare, preferably between 1 g and 1 kg of active ingredient perhectare, especially preferred between 50 g and 300 g of activeingredient per hectare depending on different parameters such as thespecific active ingredient applied and the plant species treated. In thetreatment of seed, amounts of from 0.001 g to 20 g per kg of seed,preferably from 0.01 g to 10 g per kg of seed, more preferably from 0.05to 2 g per kg of seed of nitrification inhibitors may be generallyrequired.

As a matter of course, if nitrification inhibitors and fertilizers (orother ingredients), or if mixtures thereof are employed, the compoundsmay be used in an effective and non-phytotoxic amount. This means thatthey are used in a quantity which allows to obtain the desired effectbut which does not give rise to any phytotoxic symptoms on the treatedplant or on the plant raised from the treated propagule or treated soilor soil substituents. For the use according to the invention, theapplication rates of fertilizers may be selected such that the amount ofapplied N is between 10 kg and 1000 kg per hectare, preferably between50 kg and 700 kg per hectare.

The nitrification inhibitor compounds according to the invention, e.g.compound I as defined herein above, or derivative thereof as definedherein above can be present in different structural or chemicalmodifications whose biological activity may differ. They are likewisesubject matter of the present invention.

The nitrification inhibitor compounds according to the invention, theirN-oxides and/or salts etc. may be converted into customary types ofcompositions, e.g. agrochemical or agricultural compositions such assolutions, emulsions, suspensions, dusts, powders, pastes and granules.

The composition type depends on the particular intended purpose; in eachcase, it should ensure a fine and uniform distribution of the compoundaccording to the invention.

Examples for composition types are suspensions (SC, 00, FS),emulsifiable concentrates (EC), emulsions (EW, EO, ES), microemulsions(ME), pastes, pastilles, wettable powders or dusts (WP, SP, SS, WS, OP,OS) or granules (GR, FG, GG, MG), which can be watersoluble or wettable,as well as gel formulations for the treatment of plant propagationmaterials such as seeds (GF). Usually the composition types (e.g. SC,00, FS, EC, WG, SG, WP, SP, SS, WS, GF) are employed diluted.Composition types such as OP, OS, GR, FG, GG and MG are usually usedundiluted.

The compositions are prepared in a known manner (see, for example, U.S.Pat. No. 3,060,084, EP 707 445 (for liquid concentrates), Browning:“Agglomeration”, Chemical Engineering, Dec. 4, 1967, 147-48, Perry'sChemical Engineer's Handbook, 4th Ed., McGraw-Hili, New York, 1963, S.8-57 und ff. WO 91/13546, U.S. Pat. Nos. 4,172,714, 4,144,050,3,920,442, 5,180,587, 5,232,701, 5,208,030, GB 2,095,558, U.S. Pat. No.3,299,566, Klingman: Weed Control as a Science (J. Wiley & Sons, NewYork, 1961), Hance et al.: Weed Control Handbook (8th Ed., BlackwellScientific, Oxford, 1989) and Mollet, H. and Grubemann, A.: Formulationtechnology (Wiley VCH Verlag, Weinheim, 2001). Compositions or mixturesmay also comprise auxiliaries which are customary, for example, inagrochemical compositions. The auxiliaries used depend on the particularapplication form and active substance, respectively.

Examples for suitable auxiliaries are solvents, solid carriers,dispersants or emulsifiers (such as further solubilizers, protectivecolloids, surfactants and adhesion agents), organic and inorganicthickeners, bactericides, anti-freezing agents, anti-foaming agents, ifappropriate colorants and tackifiers or binders (e.g. for seed treatmentformulations). Suitable solvents are water, organic solvents such asmineral oil fractions of medium to high boiling point, such as keroseneor diesel oil, furthermore coal tar oils and oils of vegetable or animalorigin, aliphatic, cyclic and aromatic hydrocarbons, e.g. toluene,xylene, paraffin, tetrahydronaphthalene, alkylated naphthalenes or theirderivatives, alcohols such as methanol, ethanol, propanol, butanol andcyclohexanol, glycols, ketones such as cyclohexanone andgamma-butyrolactone, fatty acid dimethylamides, fatty acids and fattyacid esters and strongly polar solvents, e.g. amines such asN-methylpyrrolidone.

Suitable surfactants (adjuvants, wetters, tackifiers, dispersants oremulsifiers) are alkali metal, alkaline earth metal and ammonium saltsof aromatic sulfonic acids, such as ligninsoulfonic acid (Borresperse®types, Borregard, Norway) phenolsulfonic acid, naphthalenesulfonic acid(Morwet® types, Akzo Nobel, U.S.A.), dibutylnaphthalene-sulfonic acid(Nekal® types, BASF, GermanY), and fatty acids, alkylsulfonates,alkylarylsulfonates, alkyl sulfates, laurylether sulfates, fatty alcoholsulfates, and sulfated hexa-, hepta- and octadecanolates, sulfated fattyalcohol glycol ethers, furthermore condensates of naphthalene or ofnaphthalenesulfonic acid with phenol and formaldehyde, polyoxyethyleneoctylphenyl ether, ethoxylated isooctylphenol, octylphenol, nonylphenol,alkylphenyl polyglycol ethers, tributylphenyl polyglycol ether,tristearylphenyl polyglycol ether, alkylaryl polyether alcohols, alcoholand fatty alcohol/ethylene oxide condensates, ethoxylated castor oil,polyoxyethylene alkyl ethers, ethoxylated polyoxypropylene, laurylalcohol polyglycol ether acetal, sorbitol esters, lignin-sulfite wasteliquors and proteins, denatured proteins, polysaccharides (e.g.methylcellulose), hydrophobically modified starches, polyvinyl alcohols(Mowiol® types, Clariant, Switzerland), polycarboxylates (Sokolan®types, BASF, Germany), polyalkoxylates, polyvinylamines (Lupasol® types,BASF, Germany), polyvinylpyrrolidone and the copolymers thereof.Examples of suitable thickeners (i.e. compounds that impart a modifiedflowability to compositions, i.e. high viscosity under static conditionsand low viscosity during agitation) are polysaccharides and organic andanorganic clays such as Xanthan gum (Kelzan®, CP Kelco, U.S.A.),Rhodopol® 23 (Rhodia, France), Veegum® (R.T. Vanderbilt, U.S.A.) orAttaclay® (Engelhard Corp., NJ, USA).

In specific embodiments, bactericides may be added for preservation andstabilization of the composition. Examples for suitable bactericides arethose based on dichlorophene and benzyl alcohol hemi formal (Proxel®from ICI or Acticide© RS from Thor Chemie and Kathon® MK from Rohm &Haas) and isothiazolinone derivatives such as alkylisothiazolinones andbenzisothiazolinones (Acticide® MBS from Thor Chemie).

Examples for suitable anti-freezing agents are ethylene glycol,propylene glycol, urea and glycerin. Examples for anti-foaming agentsare silicone emulsions (such as e.g. Silikon® SRE, Wacker, Germany orRhodorsil®, Rhodia, France), long chain alcohols, fatty acids, salts offatty acids, fluoroorganic compounds and mixtures thereof.

Suitable colorants are pigments of low water solubility andwater-soluble dyes, e.g. rhodamin B, C. I. pigment red 112, C. I.solvent red 1, pigment blue 15:4, pigment blue 15:3, pigment blue 15:2,pigment blue 15:1, pigment blue 80, pigment yellow 1, pigment yellow 13,pigment red 112, pigment red 48:2, pigment red 48:1, pigment red 57:1,pigment red 53:1, pigment orange 43, pigment orange 34, pigment orange5, pigment green 36, pigment green 7, pigment white 6, pigment brown 25,basic violet 10, basic violet 49, acid red 51, acid red 52, acid red 14,acid blue 9, acid yellow 23, basic red 10, basic red 108.

Furthermore odorous substances may be present in the compositions asdefined above. Such odorous substances comprise citronellynitril,citral, zertrahydrolinalool, tetrahydrogeraniol, geranonitril,beta-lonon R, rootanol, linalylacetat, morillol, and p-cresometylether.

Examples for tackifiers or binders are polyvinylpyrrolidons,polyvinylacetates, polyvinyl alcohols and cellulose ethers (Tylose®,Shin-Etsu, Japan).

Powders, materials for spreading and dusts can be prepared by mixing orconcomitantly grinding compound of formula I and, if appropriate,further active substances, with at least one solid carrier. Granules,e.g. coated granules, impregnated granules and homogeneous granules, canbe prepared by binding the active substances to solid carriers. Examplesof such suitable solid carriers are mineral earths such as silica gels,silicates, talc, kaolin, attaclay, limestone, lime, chalk, bole, loess,clay, dolomite, diatomaceous earth, calcium sulfate, magnesium sulfate,magnesium oxide, ground synthetic materials, fertilizers, such as, e.g.ammonium sulfate, ammonium phosphate, ammonium nitrate, ureas, andproducts of vegetable origin, such as cereal meal, tree bark meal, woodmeal and nutshell meal, cellulose powders and other solid carriers.

Examples for composition types are:

i) Water-soluble concentrates (SL, LS) 10 parts by weight of anitrification inhibitor such as a compound of formula I according to theinvention are dissolved in 90 parts by weight of water or in awater-soluble solvent. As an alternative, wetting agents or otherauxiliaries are added. The active substance dissolves upon dilution withwater. In this way, a composition having a content of 10% by weight ofactive substance is obtained.

ii) Dispersible concentrates (DC) 20 parts by weight of a nitrificationinhibitor such as a compound of formula I according to the invention aredissolved in 70 parts by weight of cyclohexanone with addition of 10parts by weight of a dispersant, e.g. polyvinylpyrrolidone. Dilutionwith water gives a dispersion. The active substance content is 20% byweight.

iii) Emulsifiable concentrates (EC) 15 parts by weight of anitrification inhibitor such as a compound of formula I according to theinvention are dissolved in 75 parts by weight of xylene with addition ofcalcium dodecylbenzenesulfonate and castor oil ethoxylate (in each case5 parts by weight). Dilution with water gives an emulsion. Thecomposition has an active substance content of 15% by weight.

iv) Emulsions (EW, EO, ES) 25 parts by weight of a nitrificationinhibitor such as a compound of formula I according to the invention aredissolved in 35 parts by weight of xylene with addition of calciumdodecylbenzenesulfonate and castor oil ethoxylate (in each case 5 partsby weight). This mixture is introduced into 30 parts by weight of waterby means of an emulsifying machine (Ultraturrax) and made into ahomogeneous emulsion. Dilution with water gives an emulsion. Thecomposition has an active substance content of 25% by weight.

v) Suspensions (SC, 00, FS) In an agitated ball mill, 20 parts by weightof a nitrification inhibitor such as a compound of formula I accordingto the invention are comminuted with addition of 10 parts by weight ofdispersants and wetting agents and 70 parts by weight of water or anorganic solvent to give a fine active substance suspension. Dilutionwith water gives a stable suspension of the active substance. The activesubstance content in the composition is 20% by weight.

vi) Water-dispersible granules and water-soluble granules (WG, SG) 50parts by weight of a nitrification inhibitor such as a compound offormula I according to the invention are ground finely with addition of50 parts by weight of dispersants and wetting agents and prepared aswater-dispersible or water-soluble granules by means of technicalappliances (e.g. extrusion, spray tower, fluidized bed). Dilution withwater gives a stable dispersion or solution of the active substance. Thecomposition has an active substance content of 50% by weight.

vii) Water-dispersible powders and water-soluble powders (WP, SP, SS,WS) 75 parts by weight of a nitrification inhibitor such as a compoundof formula I according to the invention are ground in a rotor-statormill with addition of 25 parts by weight of dispersants, wetting agentsand silica gel. Dilution with water gives a stable dispersion orsolution of the active substance. The active substance content of thecomposition is 75% by weight.

viii) Gel (GF) In an agitated ball mill, 20 parts by weight of anitrification inhibitor such as a compound of formula I according to theinvention are comminuted with addition of 10 parts by weight ofdispersants, 1 part by weight of a gelling agent wetters and 70 parts byweight of water or of an organic solvent to give a fine suspension ofthe active substance. Dilution with water gives a stable suspension ofthe active substance, whereby a composition with 20% (w/w) of activesubstance is obtained. 2. Composition types to be applied undiluted

ix) Oustable powders (OP, OS) 5 parts by weight of a nitrificationinhibitor such as a compound of formula I according to the invention areground finely and mixed intimately with 95 parts by weight of finelydivided kaolin. This gives a dustable composition having an activesubstance content of 5% by weight.

x) Granules (GR, FG, GG, MG) 0.5 parts by weight of a nitrificationinhibitor such as a compound of formula I according to the invention isground finely and associated with 99.5 parts by weight of carriers.Current methods are extrusion, spray-drying or the fluidized bed. Thisgives granules to be applied undiluted having an active substancecontent of 0.5-10% by weight, preferably an active substance content of0.5-2% by weight.

xi) ULV solutions (UL) 10 parts by weight of a nitrification inhibitorsuch as a compound of formula I according to the invention are dissolvedin 90 parts by weight of an organic solvent, e.g. xylene. This gives acomposition to be applied undiluted having an active substance contentof 10% by weight.

The compositions, e.g. agrochemical or agricultural compostions,generally comprise between 0.01 and 95%, preferably between 0.1 and 90%,most preferably between 0.5 and 90%, by weight of active substance. Theactive substances are employed in a purity of from 90% to 100%,preferably from 95% to 100% (according to NMR spectrum).

Water-soluble concentrates (LS), flowable concentrates (FS), powders fordry treatment (OS), water-dispersible powders for slurry treatment (WS),water-soluble powders (SS), emulsions (ES) emulsifiable concentrates(EC) and gels (GF) are usually employed for the purposes of treatment ofplant propagation materials, particularly seeds.

These compositions can be applied to plant propagation materials,particularly seeds, diluted or undiluted.

The compositions in question give, after two-to-tenfold dilution, activesubstance concentrations of from 0.01 to 60% by weight, preferably from0.1 to 40% by weight, in the ready-to-use preparations. Application canbe carried out before or during sowing.

Methods for applying or treating agrochemical or agricultural compoundsor mixtures, or compositions as defined herein, respectively, on toplant propagation material, especially seeds, the plant and/or the locuswhere the plant is growing or intended to grow are known in the art, andinclude dressing, coating, pelleting, dusting, soaking and in-furrowapplication methods of the propagation material. In a preferredembodiment, the compounds or the compositions thereof, respectively, areapplied on to the plant propagation material by a method such thatgermination is not induced, e.g. by seed dressing, pelleting, coatingand dusting.

In a preferred embodiment, a suspension-type (FS) composition may beused. Typically, a FS composition may comprise 1-800 g/l of activesubstance, 1 200 g/l surfactant, o to 200 g/l antifreezing agent, 0 to400 g/l of binder, 0 to 200 g/l of a pigment and up to 1 liter of asolvent, preferably water.

The active substances can be used as such or in the form of theircompositions, e.g. in the form of directly sprayable solutions, powders,suspensions, dispersions, emulsions, oil dispersions, pastes, dustableproducts, materials for spreading, or granules, by means of spraying,atomizing, dusting, spreading, brushing, immersing or pouring.

The application forms depend entirely on the intended purposes; it isintended to ensure in each case the finest possible distribution of theactive substances according to the invention. Aqueous application formscan be prepared from emulsion concentrates, pastes or wettable powders(sprayable powders, oil dispersions) by adding water.

To prepare emulsions, pastes or oil dispersions, the substances, as suchor dissolved in an oil or solvent, can be homogenized in water by meansof a wetter, tackifier, dispersant or emulsifier. Alternatively, it ispossible to prepare concentrates composed of active substance, wetter,tackifier, dispersant or emulsifier and, if appropriate, solvent or oil,and such concentrates are suitable for dilution with water.

The active substance concentrations in the ready-to-use preparations canbe varied within relatively wide ranges. In general, they are from0.0001 to 90%, such as from 30 to 80%, e.g. from 35 to 45% or from 65 to75% by weight of active substance. The active substances may also beused successfully in the ultra-low-volume process (ULV), it beingpossible to apply compositions comprising over 95% by weight of activesubstance, or even to apply the active substance without additives.

Various types of oils, wetters, adjuvants, herbicides, bactericides,other fungicides and/or pesticides may be added to the active substancesor the compositions comprising them, if appropriate not untilimmediately prior to use (tank mix). These agents can be admixed withthe compositions according to the invention in a weight ratio of 1:100to 100:1, preferably 1:10 to 10:1.

Adjuvants which can be used are in particular organic modifiedpolysiloxanes such as Break Thru S 240®; alcohol alkoxylates such asAtplus 245®, Atplus MBA 1303®, Plurafac LF 300® and Lutensol ON 30®;EO/PO block polymers, e.g. Pluronic RPE 2035® and Genapol B®; alcoholethoxylates such as Lutensol XP 80®; and dioctyl sulfosuccinate sodiumsuch as Leophen RA®.

In a further aspect the invention relates to a method for treating afertilizer or a composition. This treatment includes the application ofa nitrification inhibitor which is a compound of formula I as definedherein above to a fertilizer or a composition. The treatment mayaccordingly result in the presence of said nitrification inhibitor in apreparation of fertilizers or other compositions. Such treatment may,for example, result in a homogenous distribution of nitrificationinhibitors on or in fertilizer preparations. Treatment processes areknown to the skilled person and may include, for instance, dressing,coating, pelleting, dusting or soaking. In a specific embodiment, thetreatment may be a coating of nitrification inhibitors with fertilizerpreparations, or a coating of fertilizers with nitrification inhibitors.The treatment may be based on the use of granulation methods as known tothe skilled person, e.g. fluidized bed granulation. The treatment may,in certain embodiments, be performed with a composition comprising thenitrification inhibitor as defined herein above, e.g. comprising besidesthe inhibitor a carrier or a pesticide or any other suitable additionalcompound as mentioned above.

In a further specific embodiment, the present invention relates to amethod for treating seed or plant propagation material. The term “seedtreatment” as used herein refers to or involves steps towards thecontrol of biotic stresses on or in seed and the improvement of shootingand development of plants from seeds. For seed treatment it is evidentthat a plant suffering from biotic stresses such as fungal orinsecticidal attack or which has difficulties obtaining sufficientsuitable nitrogen-sources shows reduced germination and emergenceleading to poorer plant or crop establishment and vigor, andconsequently, to a reduced yield as compared to a plant propagationmaterial which has been subjected to curative or preventive treatmentagainst the relevant pest and which can grow without the damage causedby the biotic stress factor. Methods for treating seed or plantprogation material according to the invention thus lead, among otheradvantages, to an enhanced plant health, a better protection againstbiotic stresses and an increased plant yield.

Seed treatment methods for applying or treating inventive mixtures andcompositions thereof, e.g. compositions or agrochemical compositions asdefined herein above, and in particular combinations of nitrificationinhibitors as defined herein above and secondary effectors such aspesticides, in particular fungicides, insecticides, nematicides and/orbiopesticides and/or biostimulants, to plant propagation material,especially seeds, are known in the art, and include dressing, coating,film coating, pelleting and soaking application methods of thepropagation material. Such methods are also applicable to thecombinations or compositions according to the invention.

In further embodiments, the treatment of seeds is performed withcompositions comprising, besides a nitrification inhibitor according tothe present invention, e.g. compositions as defined herein above, afungicide and an insecticide, or a fungicide and a nematicide, or afungicide and a biopesticide and/or biostimulant, or an insecticide anda nematicide, or an insecticide and a biopesticide and/or biostimulant,or a nematicide and a biopesticide and/or biostimulant, or a combinationof a fungicide, insecticide and nematicide, or a combination of afungicide, insecticide and biopesticide and/or biostimulant, or acombination of an insecticide, nematicide, and biopesticide etc.

In a preferred embodiment, the agricultural composition or combinationcomprising a nitrification inhibitor according to the present invention,e.g. as defined herein above, is applied or treated on to the plantpropagation material by a method such that the germination is notnegatively impacted. Accordingly, examples of suitable methods forapplying (or treating) a plant propagation material, such as a seed, isseed dressing, seed coating or seed pelleting and alike. It is preferredthat the plant propagation material is a seed, seed piece (i.e. stalk)or seed bulb.

Although it is believed that the present method can be applied to a seedin any physiological state, it is preferred that the seed be in asufficiently durable state that it incurs no damage during the treatmentprocess. Typically, the seed would be a seed that had been harvestedfrom the field; removed from the plant; and separated from any cob,stalk, outer husk, and surrounding pulp or other non-seed plantmaterial. The seed would preferably also be biologically stable to theextent that the treatment would cause no biological damage to the seed.It is believed that the treatment can be applied to the seed at any timebetween harvest of the seed and sowing of the seed or during the sowingprocess (seed directed applications). The seed may also be primed eitherbefore or after the treatment.

Even distribution of the ingredients in compositions or mixtures asdefined herein and adherence thereof to the seeds is desired duringpropagation material treatment. Treatment could vary from a thin film(dressing) of the formulation containing the combination, for example, amixture of active ingredient(s), on a plant propagation material, suchas a seed, where the original size and/or shape are recognizable to anintermediary state (such as a coating) and then to a thicker film (suchas pelleting with many layers of different materials (such as carriers,for example, clays; different formulations, such as of other activeingredients; polymers; and colourants) where the original shape and/orsize of the seed is no longer recognizable.

An aspect of the present invention includes application of thecomposition, e.g. agricultural composition or combination comprising anitrification inhibitor according to the present invention, e.g. asdefined herein above, onto the plant propagation material in a targetedfashion, including positioning the ingredients in the combination ontothe entire plant propagation material or on only parts thereof,including on only a single side or a portion of a single side. One ofordinary skill in the art would understand these application methodsfrom the description provided in EP954213B1 and WO06/112700.

The composition, e.g. agricultural composition or combination comprisinga nitrification inhibitor according to the present invention, e.g. asdefined herein above, can also be used in form of a “pill” or “pellet”or a suitable substrate and placing, or sowing, the treated pill, orsubstrate, next to a plant propagation material. Such techniques areknown in the art, particularly in EP1124414, WO07/67042, and WO07/67044.Application of the composition, e.g. agricultural composition, orcombination comprising a nitrification inhibitor according to thepresent invention, e.g. as defined herein above, onto plant propagationmaterial also includes protecting the plant propagation material treatedwith the combination of the present invention by placing one or morepesticide- and nitrification inhibitor (NI)-containing particles next toa pesticide- and NI-treated seed, wherein the amount of pesticide issuch that the pesticide-treated seed and the pesticide-containingparticles together contain an Effective Dose of the pesticide and thepesticide dose contained in the pesticide-treated seed is less than orequal to the Maximal Non-Phytotoxic Dose of the pesticide. Suchtechniques are known in the art, particularly in WO2005/120226.

Application of the combinations onto the seed also includes controlledrelease coatings on the seeds, wherein the ingredients of thecombinations are incorporated into materials that release theingredients over time. Examples of controlled release seed treatmenttechnologies are generally known in the art and include polymer films,waxes, or other seed coatings, wherein the ingredients may beincorporated into the controlled release material or applied betweenlayers of materials, or both.

Seed can be treated by applying thereto the compound s present in theinventive mixtures in any desired sequence or simultaneously.

The seed treatment occurs to an unsown seed, and the term “unsown seed”is meant to include seed at any period between the harvest of the seedand the sowing of the seed in the ground for the purpose of germinationand growth of the plant.

Treatment to an unsown seed is not meant to include those practices inwhich the active ingredient is applied to the soil or soil substituentsbut would include any application practice that would target the seedduring the planting process.

Preferably, the treatment occurs before sowing of the seed so that thesown seed has been pre-treated with the combination. In particular, seedcoating or seed pelleting are preferred in the treatment of thecombinations according to the invention. As a result of the treatment,the ingredients in each combination are adhered on to the seed andtherefore available for pest control.

The treated seeds can be stored, handled, sowed and tilled in the samemanner as any other active ingredient treated seed.

Solutions for seed treatment (LS), suspoemulsions (SE), flowableconcentrates (FS), powders for dry treatment (DS), water-dispersiblepowders for slurry treatment (WS), water-soluble powders (SS), emulsions(ES), emulsifiable concentrates (EC) and gels (GF) are usually employedfor the purposes of treatment of plant propagation materials,particularly seeds. Preferred examples of seed treatment formulationtypes or soil application for pre-mix compositions are of WS, LS, ES,FS, WG or CS-type.

The compositions in question give, after two-to-tenfold dilution, activecomponents concentrations of from 0.01 to 60% by weight, preferably from0.1 to 40%, in the ready-to-use preparations. Application can be carriedout before or during sowing. Methods for applying or treatingcompositions or combinations comprising a nitrification inhibitoraccording to the present invention, e.g. as defined herein above on toplant propagation material, especially seeds include dressing, coating,pelleting, dusting, soaking and in-furrow application methods of thepropagation material. Preferably, compositions or combinationscomprising a nitrification inhibitor according to the present invention,e.g. as defined herein above are applied on to the plant propagationmaterial by a method such that germination is not induced, e.g. by seeddressing, pelleting, coating and dusting.

Typically, a pre-mix formulation for seed treatment applicationcomprises 0.5 to 99.9 percent, especially 1 to 95 percent, of thedesired ingredients, and 99.5 to 0.1 percent, especially 99 to 5percent, of a solid or liquid adjuvant (including, for example, asolvent such as water), where the auxiliaries can be a surfactant in anamount of 0 to 50 percent, especially 0.5 to 40 percent, based on thepre-mix formulation. Whereas commercial products will preferably beformulated as concentrates (e.g., pre-mix composition (formulation), theend user will normally employ dilute formulations (e.g. tank mixcomposition).

When employed in plant protection, the total amounts of activecomponents applied are, depending on the kind of effect desired, from0.001 to 10 kg per ha, preferably from 0.005 to 2 kg per ha, morepreferably from 0.05 to 0.9 kg per ha, in particular from 0.1 to 0.75 kgper ha. The application rates may range from about 1×10⁶ to 5×10¹⁵ (ormore) CFU/ha. Preferably, the spore concentration is about 1×10⁷ toabout 1×10¹¹ CFU/ha. In the case of (entomopathogenic) nematodes asmicrobial pesticides (e.g. Steinernema feltiae), the application ratespreferably range inform about 1×10⁵ to 1×10¹² (or more), more preferablyfrom 1×10⁸ to 1×10¹¹, even more preferably from 5×10⁸ to 1×10¹⁰individuals (e.g. in the form of eggs, juvenile or any other livestages, preferably in an infective juvenile stage) per ha.

When employed in plant protection by seed treatment, the amount ofcompositions or combinations comprising a nitrification inhibitoraccording to the present invention, e.g. as defined herein above (basedon total weight of active components) is in the range from 0.01-10 kg,preferably from 0.1-1000 g, more preferably from 1-100 g per 100kilogram of plant propagation material (preferably seeds). Theapplication rates with respect to plant propagation material preferablymay range from about 1×10⁶ to 1×10¹² (or more) CFU/seed. Preferably, theconcentration is about 1×10⁶ to about 1×10¹¹ CFU/seed. Alternatively,the application rates with respect to plant propagation material mayrange from about 1×10⁷ to 1×10¹⁴ (or more) CFU per 100 kg of seed,preferably from 1×10⁹ to about 1×10¹¹ CFU per 100 kg of seed.

The present invention is further illustrated by the following examples.

EXAMPLES Example 1

The compounds of the invention have been tested as follows in terms ofthe inhibition of nitrification:

100 g soil is filled into 500 ml plastic bottles (e.g. soil sampled fromthe field) and is moistened to 50% water holding capacity. The soil isincubated at 20° C. for two weeks to activate the microbial biomass. 1ml test solution, containing the compound in the appropriateconcentration (usually 0.3 or 1% of nitrogen N), or DMSO and 10 mgnitrogen in the form of ammoniumsulfate-N is added to the soil andeverything mixed well. Bottles are capped but loosely to allow airexchange. The bottles are then incubated at 20° C. for 0 and 14 days.

For analysis, 300 ml of a 1% K₂SO₄-solution is added to the bottlecontaining the soil and shaken for 2 hours in a horizontal shaker at 150rpm. Then the whole solution is filtered through a filter(Macherey-Nagel Filter MN 807 ¼). Ammonium and nitrate content is thenanalyzed in the filtrate in an autoanalyzer at 550 nm (Merck, AA11).

The inhibition (NI@a specified concentration) is calculated as follows:

${{inhibition}{in}\%} = {\frac{\left( {{{NO}3} - N_{{without}{NI}{at}{end}{of}{incubation}} - {{NO}3} - N_{{with}{NI}{at}{end}{of}{incubation}}} \right)}{\left( {{{NO}3} - N_{{without}{NI}{at}{end}{of}{incubation}} - {{NO}3} - N_{{at}{beginning}}} \right)} \times 100}$

The following compounds of general formula I.1(i) have been tested.

No. R¹ RN NI* @ 1% NI* @ 0.3% 1 C₂H₅ C(═O)CH₃ 63.7 26.6 2 CH₃ C(═O)CH₃63.8 34 3 benzyl C(═O)CH₃ 21.2 — *In each case the best obtained NIvalue is provided (only compounds with values >20).

Further, the following compounds of general formula I.3(i) have beentested.

No. R¹ RN NI* @ 1% NI* @ 0.3% 4 CH₃ C(═O)CH₃ 73.3 35.4 5 CH₃C(═O)OC(CH₃)₃ 37.8 — *In each case the best obtained NI value isprovided (only compounds with values >20).

Further, the following compounds of general formula I.3(ii) have beentested.

No. R¹ R² RN NI* @ 1% NI* @ 0.3% 6 CH₃ CH₃ C(═O)CH₃ 90.7 75.7 7 C₂H₅ CH₃CH₂OH 74.2 57.9 8 CH₃ CH₃ CH(C(═O)OH)CH₂(C(═O)OH) 53.0 — 9 C₂H₅ CH₃CH(C(═O)OH)CH₂(C(═O)OH) 42.7 — *In each case the best obtained NI valueis provided (only compounds with values >20).

1. An N-functionalized alkoxy pyrazole compound of formula I

or a salt, stereoisomer, tautomer, or N-oxide thereof, wherein R¹ is H,C₁-C₆-alkyl, C₃-C₆-cycloalkyl, benzyl, allyl, CHR^(a)C(═O)OR^(b),CHR^(a)C(═O)NR^(b)R^(c) or phenyl, wherein said phenyl group isunsubstituted or substituted by one or more, same or differentsubstituents R^(x); R² is halogen, C₁-C₆-alkyl, C₃-C₆-cycloalkyl,benzyl, allyl, propargyl, or phenyl, wherein said phenyl group isunsubstituted or substituted by one or more, same or differentsubstituents R^(x); R^(N) is C₁-C₆-akyl C₃-C₆-cycloalkyl, benzyl, allyl,or phenyl, wherein said groups are unsubstituted or substituted by oneor more, same or different substituents R^(y); CHR^(a)C(═O)OR^(b),CHR^(a)C(═O)NR^(b)R^(c), CH(C(═O)OR^(b))CH₂(C(═O)OR^(b)); C(═O)R^(d),C(═O)OR^(b), C(═O)NR^(b)R^(c), CHR^(a)OR^(b), orCHR^(a)NR^(e)(C═O)R^(f); and wherein R^(a) is H, C₁-C₄-alkyl,C₁-C₄-haloalkyl, C₃-C₈-cycloalkyl, phenyl, or phenyl-C₁-C₂-alkyl; R^(b)is H, C₁-C₄-alkyl, C₁-C₄-haloalkyl, C₃-C₈-cycloalkyl, phenyl, orphenyl-C₁-C₂-alkyl; R^(c) is H, C₁-C₄-alkyl, C₁-C₄-haloalkyl, or phenyl;R^(d) is H, C₁-C₈-alkyl, C₂-C₈-alkenyl, C₂-C₈-alkynyl, phenyl, orphenyl-C₁-C₂-alkyl, wherein these groups are unsubstituted orsubstituted by a group COOH; R^(e) is H, C₁-C₄-alkyl, C₃-C₈-cycloalkyl,or C₆-C₁₀-aryl; R^(f) is H, or C₁-C₄-alkyl; R^(x) is halogen,C₁-C₄-alkyl, C₁-C₄-haloalkyl, C₁-C₄-alkoxy, or C₁-C₄-haloalkoxy; R^(y)is halogen, CN, OH, NO₂, COOH, NR^(b)R^(c), NR^(b)(C═O)R,C(═O)NR^(b)R^(c), C₁-C₄-alkyl, C₁-C₄-haloalkyl, C₁-C₄-alkoxy,C₁-C₄-haloalkoxy, C₁-C₄-alkylcarbonyl, C₁-C₄-alkylcarboxy,C₁-C₄-alkylthio, C₁-C₄-alkylsulfonyl, and S(O)₂NR^(b)R^(c); n is 0, 1,or
 2. 2. The compound of claim 1, wherein R¹ is C₁-C₆-alkyl, benzyl,allyl.
 3. The compound of claim 1, wherein n is 0; or n is 1, and R² isC₁-C₃-alkyl or phenyl.
 4. The compound of claim 1, wherein R^(N) isC(═O)R^(d), CHR^(a)C(═O)OR^(b), CHR^(a)C(═O)NR^(b)R^(c),CH(C(═O)OR^(b))CH₂(C(═O)OR^(b)), or CHR^(a)NR^(e)(C═O)R^(f).
 5. Thecompound of claim 1, wherein R^(a) is H; R^(b) is H or C₁-C₄-alkyl;R^(e) is H or C₁-C₄-alkyl; R^(d) is C₁-C₃-alkyl; R^(e) is H; R^(f) is Hor CH₃.
 6. A composition comprising at least one compound of formula Ias defined in claim 1 and at least one carrier.
 7. The compound of claim1, wherein said reduction of nitrification occurs in or on a plant, inthe root zone of a plant, in or on soil or soil substituents and/or atthe locus where a plant is growing or is intended to grow.
 8. A methodfor reducing nitrification, comprising treating a plant growing on soilor soil substituents and/or the locus or soil or soil substituents wherethe plant is growing or is intended to grow, with at least one compoundof formula I as defined in claim
 1. 9. The method of claim 8, whereinthe plant and/or the locus or soil or soil substituents where the plantis growing or is intended to grow is additionally provided with afertilizer.
 10. The method of claim 9, wherein the application of saidcompound of formula I and of said fertilizer is carried outsimultaneously or with a time lag.
 11. A method for treating afertilizer, comprising applying a nitrification inhibitor as defined inclaim 1 to the fertilizer.
 12. The agrochemical mixture of claim 7,wherein said fertilizer is a solid or liquid ammonium-containinginorganic fertilizer; a solid or liquid organic fertilizer, or anurea-containing fertilizer.
 13. The method of claim 8, wherein saidplant is an agricultural plant, a vegetable; sorghum; a silviculturalplant; an ornamental plant; or a horticultural plant, each in itsnatural or in a genetically modified form.
 14. The method of claim 10,wherein the time lag is 1 day, 2 days, 3 days, 1 week, 2 weeks, or 3weeks.
 15. The agrochemical mixture of claim 12, wherein the fertilizeris selected from the group consisting of an NPK fertilizer, ammoniumnitrate, calcium ammonium nitrate, ammonium sulfate nitrate, ammoniumsulfate, ammonium phosphate, liquid manure, semi-liquid manure, biogasmanure, stable manure, straw manure, worm castings, compost, seaweed,guano, urea, formaldehyde urea, anhydrous ammonium, urea ammoniumnitrate (UAN) solution, urea sulphur, urea based NPK-fertilizers, orurea ammonium sulfate.
 16. The method of claim 13, wherein theagricultural plant or vegetable is selected from the group consisting ofwheat, barley, oat, rye, soybean, corn, potatoes, oilseed rape, canola,sunflower, cotton, sugar cane, sugar beet, rice, spinach, lettuce,asparagus, and cabbage.